Lecture 3
chemical balance. The law of active masses. Chemical equilibrium constant and methods of its expression.
Chemical equilibrium
In most cases, chemical reactions do not proceed so deeply that the reactants are completely converted into products. The reactions proceed to equilibrium, at which the system contains both products and unreacted starting substances, and there is no further tendency to change their concentrations. Sometimes the amount of product in the equilibrium mixture is so much greater than the amount of unreacted starting materials that, from a practical point of view, the reaction is completed. Only such reactions reach the end in practice, in which at least one of the products is removed from the reaction sphere (for example, it precipitates or is released from solution in the form of a gas). But in many important cases, the reaction mixture at equilibrium contains significant concentrations of both products and starting materials.
Chemical equilibrium- this is a thermodynamic equilibrium in a system in which direct and reverse chemical reactions are possible.
There are thermodynamic and kinetic criteria for chemical equilibrium. From a kinetic point of view, at chemical equilibrium, the rates of all reactions proceeding in two opposite directions are equal to each other, therefore, no change in macroscopic parameters, including the concentrations of reactants, is observed in the system.
From a thermodynamic point of view, chemical equilibrium is characterized by the achievement of a minimum and time-invariant value of the Gibbs energy (or Helmholtz energy).
Knowledge of the basic laws of the doctrine of chemical equilibrium is absolutely necessary for a chemist-technologist. In industry, for example, in chemical and pharmaceutical plants, it is useless to build complex plants for the production of certain substances if thermodynamic calculations show that the reaction tends to go in the "wrong" direction. In addition, when determining the efficiency and profitability of production, it is necessary to know how to obtain the maximum yield of the target product.
The actual mechanism of both the forward and reverse reactions is in many cases complex and often not known in detail or completely. Fortunately for chemists, it is not necessary to know the actual mechanism of a reaction in order to draw correct conclusions about the course of chemical processes.
The prediction of the direction of a chemical reaction, as well as the calculation of the theoretical equilibrium yield of its products and the composition of the equilibrium reaction mixture depending on the initial composition, temperature and pressure, is the main task of the study of chemical equilibrium.
Equilibrium constant
An arbitrary reversible chemical reaction can be described by an equation of the form:
aA + bB Û dD + eE
In accordance with the law of mass action, in the simplest case, the rate of a direct reaction is related to the concentrations of the starting substances by the equation
vpr = k etc FROM Ah FROM Bb,
and the rate of the reverse reaction - with the concentrations of the products by the equation
vrev = cobr FROM Dd FROM E.e.
When equilibrium is reached, these speeds are equal to each other:
vpr = vrev
The ratio of the rate constants of the forward and reverse reactions to each other will be equal to equilibrium constant:
Since this expression is based on taking into account the amount of reactants and reaction products, it is a mathematical notation of the law acting masses for reversible reactions.
The equilibrium constant, expressed in terms of the concentrations of the reacting substances, is called the concentration constant and is denoted Ks . For a more rigorous consideration, instead of concentrations, one should use the thermodynamic activities of substances a = fC (where f - activity coefficient). In this case, we are talking about the so-called thermodynamic equilibrium constant
At low concentrations, when the activity coefficients of the starting substances and products are close to unity, Ks and Ka practically equal to each other.
The equilibrium constant of a reaction occurring in the gas phase can be expressed in terms of partial pressures R substances involved in the reaction:
Between Cr and Ks there is a relation that can be derived in this way. We express the partial pressures of substances in terms of their concentrations using the Mendeleev-Clapeyron equation:
pV = nRT ,
where p = (n /V )RT = CRT .
Then for the reaction in general form, after replacing partial pressures by concentrations, we obtain
Replacing the expression (d + c) - (a + b) with its equal D n , we get the final expression
Cr = Ks (RT )D n or Ks = Cr (RT )-D n ,
where D n - change in the number of moles of gaseous substances during the reaction:
D n = å ni prod (g) - å ni ref (g) ).
If a D n = 0, i.e. the process goes on without changing the number of moles of gaseous substances, and Cr = Ks .
For example, for the ethylene hydration reaction occurring in the gas phase:
C2H4 (g) + H2O (g) Û C2H5OH (g),
In this case D n = 1 - (1 + 1) = -1. Hence, the relation between the constants can be expressed by the following equation:
Cr = Ks (RT )- 1 or Ks = Cr RT .
Thus, knowing Cr this reaction at any given temperature, you can calculate the value Ks and vice versa.
Calculations using equilibrium constants
Equilibrium constants are mainly used to answer the following questions:
1. Should the reaction proceed spontaneously under certain conditions?
2. What will be the concentration of products (equilibrium yield) after equilibrium is established in the system?
Determination of the direction of reversible reactions
Since the equilibrium constant is the ratio of the rate constants of the forward and reverse reactions, its very value indicates the direction of the process. So, if the equilibrium constant is greater than one, then under these conditions the direct reaction will spontaneously occur, but if it is less than one, the reverse reaction.
In accordance with the Le Chatelier principle, the equilibrium position can be shifted by changing the conditions under which the reaction proceeds. Therefore, in the general case, it is possible to estimate the shift in equilibrium with a change in the ratio of the initial amounts of substances participating in the reaction. If the ratio of the concentrations of the reactants at the initial moment is denoted P :
then according to the ratio Z and Ks it is possible to predict the direction of the reaction under given experimental conditions:
at P < K the direct reaction proceeds spontaneously;
at P > K the reverse reaction proceeds spontaneously;
at P = K the system is in equilibrium.
The more the value of the equilibrium constant differs from unity, the more the equilibrium of the reaction is shifted in the corresponding direction (to the right at To > 1 and to the left at To < 1).
Factors affecting the balance. Le Chatelier's principle-
Brown
At equilibrium, the forward and reverse reactions exactly cancel each other out. But how sensitive is this compensation to changes in reaction conditions? How can the state of equilibrium be changed? These issues are of great practical importance if it is required to increase the yield of a useful reaction product, for example, a drug, or, conversely, to reduce the yield of an undesirable product.
If it is possible to continuously withdraw products from the reaction mixture (solution) in the form of a gas or precipitate, as well as using such technological operations as freezing, washing out, etc., then the reacting system can thereby be constantly kept in a non-equilibrium, unbalanced state. Under these conditions, there is a need for ever new quantities of reagents and there is a continuous formation of products. This way of breaking the equilibrium in the direction of obtaining the desired product is carried out without changing the equilibrium constant. But it is often possible to increase the yield of products by increasing the equilibrium constant.
One way to increase the equilibrium constant is to change the temperature. Since in most cases the rates of the forward and reverse reactions depend on T , the equilibrium constant also exhibits a temperature dependence. Strictly speaking, a change in temperature simultaneously changes the rate of both the forward and reverse reactions. But, if an increase in temperature accelerates the forward reaction to a greater extent than the reverse, then the equilibrium constant will increase.
The temperature dependence of the equilibrium position is one example of the general principle of dynamic chemical equilibrium called Le Chatelier's principle(or Le Chatelier - Brown):
If an external influence is exerted on a system in a state of chemical equilibrium, the equilibrium position is shifted in such a way as to counteract the effect of this influence. .
Le Chatelier's principle also applies to other ways of influencing equilibrium, for example, to changing pressure, but it has a qualitative character. Quantitatively, the dependence of the equilibrium constant of the reaction on various factors is expressed by the equations of the isotherm, isobar and isochore of the chemical reaction, derived by J. van't Hoff.
Influence on the equilibrium of the initial composition of the reaction
mixtures. Chemical reaction isotherm equation
The maximum work of a reaction proceeding in the gas phase at constant temperature and pressure is the algebraic sum of the work performed by all substances participating in the reaction during the transition from initial partial pressures to equilibrium ones.
Let us consider the gas reaction expressed in general form by the equation
aA + bB Û dD + eE.
Pressure R in the system using the Mendeleev-Clapeyron equation can be expressed in terms of volume V and temperature T :
p = nRT /V ,
whence, assuming that the total number of moles of all components is 1, we obtain for the expansion work
pdV = (RT /V )dV ,
Since the maximum useful work can be calculated by integrating the expression: V2
A'max = ò pdV ,
we get
and since A'max = -D Gr ,
then you can write:
For processes proceeding at a constant volume, similar expressions can be obtained, which include the maximum work and the change in the Helmholtz energy during the reaction. In this case, partial pressures are replaced by the initial concentrations of substances:
Equations (4.1) - (4.4), derived by J. van't Hoff, are called chemical reaction isotherm equations. They make it possible to determine in which direction and to what extent the reaction can proceed under the conditions under consideration for a given composition of the reaction mixture at a constant temperature.
For standard conditions, when the initial partial pressures (or initial concentrations or activities) of all substances participating in the reaction are equal to unity, the isotherm equations will look like this:
BUT 'max = RT ln Kp ; D Gor = - RT ln Kp (4.5)
BUT max = RT ln K With ; D BUT o r = - RT ln K With .
It follows that, by defining the standard value D Gor or D BUT o r for a reaction, one can easily calculate its equilibrium constant.
Effect on equilibrium yield of volume change
and pressure of the reaction mixture
For reactions taking place in the gas phase, the change in the volume of the reaction mixture can be judged by the change in the number of moles of the reactants
D n = å ni prod - å ni ref
There are three cases corresponding to different types of chemical reactions:
a) D n < 0 (реакция идет с уменьшением объёма). Например, реакция синтеза аммиака :
N2 (g) + 3H2 (g) Û 2NH3 (g) ; D n = 2 - (1 + 3) = -2
In accordance with the Le Chatelier principle, a decrease in volume (with an increase in pressure) will shift the equilibrium of this and similar reactions to the right, and an increase in volume (with a decrease in pressure) - to the left.
b) D n > 0 (the reaction proceeds with an increase in volume). For example, the decomposition reaction of methanol:
CH3OH (g) Û CO (g) + 2H2 (g) ; D n = (1 + 2) - 1 = 2
In this case, a decrease in volume (or an increase in pressure) will shift the equilibrium to the left, and an increase in volume (with a decrease in pressure) will shift it to the right.
in) D n = 0 (reaction proceeds without volume change). For example, the reaction of chlorine with hydrogen bromide:
Cl2 (g) + 2HBr (g) Û Br2 (g) + 2HCl (g) ; D n = (1 + 2) - (1 + 2) = 0
A change in the volume (pressure) of the reaction mixture does not affect the yield of the products of such reactions.
Chemical equilibrium in heterogeneous systems
The regularities considered earlier relate mainly to homogeneous reactions, i.e., to reactions involving substances that are in the same physical state - in the form of a gas or in the form of a solution. Equilibria in which substances that are in two or more physical states take part (for example, a gas with a liquid or with a solid) are called heterogeneous equilibria.
As an example, consider the decomposition of calcium carbonate CaCO3, used in pharmacy as an antacid (deacidification). This is a convenient model for considering the decomposition of various solid substances, including drugs, with the formation of gaseous products:
CaCO3 (t) Û CaO (t) + CO2 (g)
In accordance with the law of mass action, the expression for the equilibrium constant of this reaction can be written as follows:
The partial pressures of CaO and CaCO3 in the gas phase, firstly, are very small, and secondly, they remain practically constant at any moment of the reaction. This means that as long as solid CaCO3 and CaO are in contact with the gas, their effect on the equilibrium will be unchanged. In this case, the equilibrium constant does not depend on the amount of the solid phase. It is possible to divide both parts of the expression for the equilibrium constant by the value p CaO/ p CaCO3 and accept that
K ’ p = p CO2,
where K ’ p = Kp p CaC03/ p CaO - modified equilibrium constant; in this case, the partial pressures of CaCO3 and CaO enter into the quantity K ’ p implicitly.
If the partial pressure of CO2 over CaCO3, at a given temperature, is kept lower than the value K ’ p , then all CaCO3 will turn into CaO and CO2; if the partial pressure p CO2 more than K ’ p , then all CaO will turn into CaCO3. The equilibrium partial pressure of CO2, equal to K ’ p at this temperature is called dissociation pressure.
When the CO2 pressure reaches 1 atm, the equilibrium in this reaction shifts towards the dissociation of CaCO3, i.e., the decomposition of calcium carbonate. this happens at a temperature of 897 ° C:
Similar reasoning and the concept of dissociation pressure can be extended to other heterogeneous reactions involving solids. In the event that a medicinal substance (in powder or tablets) can react with gases in the air (H2O, O2, CO2), or decompose with their release, it is necessary to ensure that the partial pressure of these gases and vapors in the warehouse atmosphere is less than the dissociation pressure (or the corresponding equilibrium constant K ’ p ).
1 . Determine the constant of chemical equilibrium of the process of dissociation of phosphorus pentachloride, proceeding according to the equation PCl 5<=>PCl 3 + Cl 2,
according to equilibrium concentrations of K C and partial pressures of components K R. It is known that by the time equilibrium was established at a temperature of 500 K, 54% of PCl 5 had reacted with respect to the initial concentration of 1 mol/l.
Solution. According to the law of mass action for chemical equilibrium
K C = :.
Applying this expression to our equation, we get
K C \u003d C μ (PCl 3) C μ (Cl 2) / C μ (PCl 5).
This expression includes the equilibrium concentrations of the reactant and products. Let's calculate them.
If by the time equilibrium is established, 54% of phosphorus pentachloride has reacted, then 46% is still left in the system, which means that the equilibrium concentration of PCl 5 will be: C μ (PCl 5) = C 0 (PCl 5) 0.46 = 1 0, 46 = 0.46 (mol/l).
Before the start of the reaction, there were no products in the reaction space; therefore, their concentration in the equilibrium state is determined by the proportion of the spent reagent (see the reaction equation), i.e. C μ (PCl 3) \u003d C μ (Cl 2) \u003d 0.54 mol / l.
Let's substitute the found values into the expression for К С and make calculations:
K C \u003d (0.54) (0.54) / (0.46) \u003d 0.63 (mol / l).
The equilibrium constant in relation to the partial pressures of the gas system is determined by the equation: K R = K C (RT) Δ n, while Δn = Σn prod - Σn react. From the chemical equation it can be seen that Δn = 2 - 1 = 1 mol.
We substitute the found and known values \u200b\u200bin the expression for K P and make calculations: K P \u003d (0.63) (8.31 500) 1 \u003d 2617 (Pa / l K) \u003d 2.62 (kPa / l K ).
Answer: K C = 0.63 mol/l; K P \u003d 2.62 kPa / l K.
2 . In a state of system equilibrium
CO 2 (g) + H 2 (g)<=>CO (g) + H 2 O (g)
the reaction mixture had the following composition by volume: 22% CO 2 , 41% H 2 , 17% CO, and 20% H 2 O. Determine K P and K C for this equilibrium at 1900 K and a pressure of 98,501 Pa.
Solution. From the volume fractions of each gas in a mixture, one can determine their partial pressures, knowing that the total pressure in any gas mixture is equal to the sum of the partial pressures of the gases that make up this mixture:
P \u003d P (CO 2) + P (H 2) + P (CO) + P (H 2 O).
And then P (CO 2) \u003d 0.22 P \u003d 0.22 98 501 \u003d 21 670 (Pa);
P (H 2) \u003d 0.41 98 501 \u003d 40 385 (Pa);
Р(СО) = 0.17 98 501 = 16 745 (Pa); P (H 2 O) \u003d 0.2 98 501 \u003d 19 700 (Pa).
We introduce the found values of the partial pressures of gases into the equation that establishes the dependence of the equilibrium constant on the partial pressures of the process components:
K P \u003d P (CO) P (H 2 O) / P (CO 2) P (H 2);
K P \u003d 16745 19700 / 21670 40385 \u003d 0.38.
The equilibrium constant in relation to the equilibrium concentrations of reagents K C is calculated by the equation K C = K R ·(RT) -Δ n . For our case, Δn = 2 - 2 = 0, therefore, the factor (RT) -Δ n = (RT) 0 = 1. and then K C = K P = 0.38.
Answer: K C = K P = 0.38.
3 . Equilibrium in a homogeneous system
4HCl (g) + O 2 (g)<=>2H 2 O (g) + 2Cl 2 (g)
established at the following concentrations of reactants (mol/l): C μ (H 2 O) = 0.14; C μ (Cl 2) = 0.14; C μ (HCl) = 0.20; C μ (O 2) = 0.32. Calculate the equilibrium constant of this reaction and determine the initial concentrations of hydrogen chloride and oxygen.
Solution. According to the law of mass action, the chemical equilibrium constant for the concentrations of reagents is determined in relation to our case by the equation:
K C \u003d [C μ 2 (H 2 O) C μ 2 (Cl 2)] / [C μ 4 (HCl) C μ (O 2)].
Substituting the values of equilibrium concentrations into it and performing calculations, we obtain:
K C \u003d (0.14) 4 / (0.20) 4 (0.32) \u003d 0.75 (l / mol).
The chemical equation of the reaction shows in what proportions the substances interact with each other: from 4 mol of HCl and 1 mol of O 2, 2 mol of H 2 O and Cl 2 are formed. This means that ΔС μ (HCl) = 2 0.14 = 0.28 mol / l and ΔС μ (О 2) = ½ 0.14 = 0.07 mol / l .
The initial concentrations of hydrogen chloride and oxygen will be equal to:
C μ 0 (HCl) \u003d C μ (HCl) + ΔC μ (HCl), C μ 0 (HCl) \u003d (0.20 + 0.28) mol / l \u003d 0.48 mol / l;
C μ 0 (O 2) \u003d C μ (O 2) + ΔC μ (O 2), C μ 0 (O 2) \u003d (0.32 + 0.07) mol / l \u003d 0.39 mol / l.
Answer: equilibrium constant of this reaction K C = 0.75 l / mol; initial concentrations of reagents С μ 0 (HCl) = 0.48 mol/l; C μ 0 (O 2) = 0.39 mol / l.
4 . Determine the equilibrium constant of the reaction
2NO(g) + Cl 2 (g)<=>2NOCl(g)
at a temperature of 298 K according to the values of the standard enthalpies of formation and the entropies of its participants.
Solution. The dependence of the equilibrium constant of a chemical reaction on temperature is determined according to the Kirchhoff equation:
ΔH˚ equal ΔS˚ equal
ℓnК Р = – – + – .
We calculate ΔH˚ equal and ΔS˚ equal under standard conditions, using the reference data of the table in Appendix No. 1:
ΔH˚ equals = 2ΔН 0 (NOCl) - 2ΔН 0 (NO),
ΔS˚ equals = 2S 0 (NOCl) - 2S 0 (NO) - S 0 (Cl 2), then
ΔH˚ equals = 2 53.55 kJ / mol - 2 90.37 kJ / mol \u003d - 73.64 kJ / mol \u003d - 73640 J / mol;
ΔS˚ equals = 2 263.6 (J / mol K) - 2 210.62 (J / mol K) - 223.0 (J / mol K) \u003d - 117.04 J / mol K .
We substitute the found values into the Kirchhoff equation and perform the calculations:
ℓnK P \u003d - (- 73640) / 8.31 298 + (-117.04 / 8.31) \u003d 29.74 - 14.08 \u003d 15.66.
Then K R \u003d e 15.66 \u003d 5.7 10 6.
Answer: equilibrium constant of the reaction K P = 5.7 10 6 .
5 . For the reaction H 2 (g) + Br 2 (g)<=>2HBr(g) at some temperature, the equilibrium constant is equal to one. Determine the composition (in percent by volume) of the equilibrium gas reaction mixture if the initial mixture consisted of 3 moles of hydrogen and 2 moles of bromine.
Solution. Let us write down the expression of the law of mass action for the equilibrium state of the system:
Kp \u003d C 2 μ (HBr) / C μ (H 2) C μ (Br 2) \u003d 1.
Let us assume that by the time equilibrium is established in the system, it has reacted according to X moles of H 2 and Br 2. Then their equilibrium concentrations will be equal: C μ (H 2) = (3 - X) mol, C μ (Br 2) = (2 - X) mol. Accordingly, by this moment, 2 X mole of hydrogen bromide, i.e. With μ (HBr) = 2 X mol.
Substituting these values of equilibrium concentrations into the expression for the equilibrium constant, we obtain an equation with one unknown: (2 X) 2 /(3-X)·(2- X) = 1.
Deciding it about X, we get: 3 X 2 - 5X - 6 = 0;
X 1.2 = (-5±√25+72)/6 = (-5±10)/6. From here X= 0.75 mol.
Thus, at the moment of equilibrium in the mixture were present: 2.25 mol H 2 , 1.25 mol Br 2 and 1.50 mol HBr, which corresponds to 45% hydrogen, 25% bromine and 30% hydrogen bromide.
Answer: at equilibrium, the gas mixture included 45% H 2 , 25% Br 2 and 30% HBr.
Consider a reversible chemical reaction of a general form, in which all substances are in the same state of aggregation, for example, liquid:
aA + bB D cC + d D,
where A and B are the starting materials of the direct reaction; C and D are direct reaction products; a, b, c, and d- stoichiometric coefficients.
At the initial moment of time, when the concentration of substances A and B is the highest, the rate of the direct reaction will also be the highest and, according to the law of mass action, is equal to
u pr \u003d k 1 C A a C B in (6.1)
where k 1 is the rate constant of the direct reaction.
Over time, the concentration of substances A and B decreases, and, consequently, the rate of the direct reaction also decreases.
At the initial moment of time, the concentration of substances C and D is equal to zero, and, consequently, the rate of the reverse reaction is equal to zero, over time, the concentration of substances C and D increases, and, consequently, the rate of the reverse reaction also increases and it will be equal to
u arr \u003d k 2 C C with C D d (6.2)
where k 2 is the rate constant of the reverse reaction.
At the moment of reaching equilibrium, the concentrations take on the value of equilibrium, and the speeds are equal to each other u pr \u003d u arr, therefore
k 1 C A a C B c = k 2 C C c C D d (6.3)
Let's move the rate constants in one direction, and the concentrations in the other:
The ratio of two constants is a constant, and it is called the constant of chemical equilibrium:
The equilibrium constant shows how many times the rate of the forward reaction is greater or less than the rate of the reverse reaction.
Equilibrium constant is the ratio of the product of the equilibrium concentrations of the reaction products, taken to the power of their stoichiometric coefficients, to the product of the equilibrium concentrations of the starting materials, taken to the power of their stoichiometric coefficients.
The value of the equilibrium constant depends on the nature of the reacting substances and temperature, and does not depend on the concentration at the moment of equilibrium, since their ratio is always a constant value, numerically equal to the equilibrium constant. If a homogeneous reaction occurs between substances in solution, then the equilibrium constant is denoted by K C, and if between gases, then K P.
where Р С, Р D , Р А and Р В are the equilibrium pressures of the reaction participants.
Using the equation Clapeyron-Mendeleev, you can determine the relationship between K P and K C
Move the volume to the right side
p = RT, i.e. p = CRT (6.9)
We substitute equation (6.9) into (6.7), for each reagent and simplify
where Dn is the change in the number of moles of gaseous participants in the reaction
Dn = (s + d) - (a + c) (6.11)
Consequently,
K P \u003d K C (RT) D n (6.12)
From equation (6.12) it can be seen that K P = K C, if the number of moles of gaseous participants in the reaction does not change (Dn = 0) or there are no gases in the system.
It should be noted that in the case of a heterogeneous process, the concentration of the solid or liquid phase in the system is not taken into account.
For example, the equilibrium constant for a reaction of the form 2A + 3B \u003d C + 4D, provided that all substances are gases and has the form
and if D is solid, then
The equilibrium constant is of great theoretical and practical importance. The numerical value of the equilibrium constant makes it possible to judge the practical possibility and depth of a chemical reaction.
If K > 1, then this reaction proceeds with a significant yield of reaction products; if K > 10 4 , then the reaction is irreversible; if K< 1, то такая реакция нетехнологична; если K < 10 -4 , то такая реакция невозможна.
Knowing the equilibrium constant, one can determine the composition of the reaction mixture at the moment of equilibrium and calculate the yield constant of the reaction products. The equilibrium constant can be determined using experimental methods, by analyzing the quantitative composition of the reaction mixture at the moment of equilibrium, or by applying theoretical calculations. For many reactions under standard conditions, the equilibrium constant is a tabular value.
6.3. Factors affecting chemical equilibrium. Le Chatelier's principle
Under external action on the system, the chemical equilibrium is shifted, i.e., the equilibrium concentrations of the initial substances and reaction products change. If, as a result of an external influence, the equilibrium concentrations of the reaction products increase, then they speak of a shift of the equilibrium to the right (in the direction of the direct reaction). If, due to external influence, the equilibrium concentrations of the initial substances increase, then they speak of a shift of the equilibrium to the left (in the direction of the reverse reaction).
The influence of various factors on the shift in chemical equilibrium reflects Le Chatelier's principle (1884): if a system in stable chemical equilibrium is acted upon from the outside by changing temperature, pressure or concentration, then the chemical equilibrium shifts in the direction in which the effect of the effect produced decreases.
It should be noted that the catalyst does not shift the chemical equilibrium, but only accelerates its onset.
Consider the influence of each factor on the shift of chemical equilibrium for a general reaction:
aA + bB = cC + d D±Q.
Effect of concentration change. According to the Le Chatelier principle, an increase in the concentration of one of the components of an equilibrium chemical reaction leads to a shift in the equilibrium towards an increase in the reaction in which the chemical processing of this component occurs. Conversely, a decrease in the concentration of one of the components leads to a shift in the equilibrium towards the formation of this component.
Thus, an increase in the concentration of substance A or B shifts the equilibrium in the forward direction; an increase in the concentration of substance C or D shifts the equilibrium in the opposite direction; a decrease in the concentration of A or B shifts the equilibrium in the opposite direction; a decrease in the concentration of substance C or D shifts the equilibrium in the forward direction. (Schematically, you can write: -C A or C B ®; -C C or C D ¬; ¯ C A or C B ¬; ¯ C C or CD ®).
The effect of temperature. The general rule that determines the effect of temperature on equilibrium has the following formulation: an increase in temperature contributes to a shift in equilibrium towards an endothermic reaction (- Q); lowering the temperature contributes to a shift in the equilibrium towards an exothermic reaction (+ Q).
Reactions that proceed without thermal effects do not shift the chemical equilibrium with a change in temperature. An increase in temperature in this case only leads to a more rapid establishment of equilibrium, which would be achieved in the given system even without heating, but over a longer time.
Thus, in an exothermic reaction (+ Q), an increase in temperature leads to a shift in the equilibrium in the opposite direction and, conversely, in an endothermic reaction (- Q), an increase in temperature leads to a shift in the forward direction, and a decrease in temperature in the opposite direction. (Schematically, you can write: at +Q -T ¬; ¯T ®; at -Q -T ®; ¯T ¬).
Influence of pressure. As experience shows, pressure has a noticeable effect on the displacement of only those equilibrium reactions in which gaseous substances participate, and in this case, the change in the number of moles of gaseous participants in the reaction (Dn) is not equal to zero. With an increase in pressure, the equilibrium shifts towards the reaction that is accompanied by the formation of a smaller number of moles of gaseous substances, and with a decrease in pressure, towards the formation of a greater number of moles of gaseous substances.
Thus, if Dn = 0, then pressure does not affect the shift in chemical equilibrium; if Dn< 0, то увеличение давления смещает равновесие в прямом направлении, уменьшение давления в сторону обратной реакции; если Dn >0, then an increase in pressure shifts the equilibrium in the opposite direction, and a decrease in pressure - in the direction of a direct reaction. (Schematically, it can be written: at Dn = 0 P does not affect; at Dn 0 -P ¬, ¯P ®). Le Chatelier's principle is applicable to both homogeneous and heterogeneous systems and gives a qualitative characteristic of an equilibrium shift.
An arbitrary reversible chemical reaction can be described by an equation of the form:
aA + bB Û dD + eE
In accordance with the law of mass action, in the simplest case, the rate of a direct reaction is related to the concentrations of the starting substances by the equation
v pr = k pr C A a FROM in b,
and the rate of the reverse reaction - with the concentrations of the products by the equation
v arr = k arr C D d FROM E e .
When equilibrium is reached, these speeds are equal to each other:
v pr = v arr
The ratio of the rate constants of the forward and reverse reactions to each other will be equal to equilibrium constant:
Since this expression is based on taking into account the amount of reactants and reaction products, it is a mathematical notation of the law acting masses for reversible reactions.
The equilibrium constant, expressed in terms of the concentrations of the reactants, is called the concentration constant and is denoted K s . For a more rigorous consideration, instead of concentrations, one should use the thermodynamic activities of substances a = fC (where f - activity coefficient). In this case, we are talking about the so-called thermodynamic equilibrium constant
At low concentrations, when the activity coefficients of the starting substances and products are close to unity, K s and K a practically equal to each other.
The equilibrium constant of a reaction occurring in the gas phase can be expressed in terms of partial pressures R substances involved in the reaction:
Between K r and K s there is a relation that can be derived in this way. We express the partial pressures of substances in terms of their concentrations using the Mendeleev-Clapeyron equation:
pV = nRT ,
where p = (n /V )RT = CRT .
Then for the reaction in general form, after replacing partial pressures by concentrations, we obtain
Replacing the expression (d + c) - (a + b) with its equal Dn , we get the final expression
K r = K s (RT )D n or K s = K r (RT ) - D n ,
where Dn - change in the number of moles of gaseous substances during the reaction:
Dn = ån i prod (g) - ån i ref (r) ).
If a Dn = 0, i.e. the process goes on without changing the number of moles of gaseous substances, and K r = K s .
For example, for the ethylene hydration reaction occurring in the gas phase:
C 2 H 4 (g) + H 2 O (g) Û C 2 H 5 OH (g),
In this case Dn = 1 - (1 + 1) = -1. Hence, the relation between the constants can be expressed by the following equation:
K r = K s (RT ) - 1 or K s = K r RT .
Thus, knowing K r this reaction at any given temperature, you can calculate the value K s and vice versa.
The dimension of the equilibrium constants depends on the method of expressing the concentration (pressure) and the stoichiometry of the reaction. Often it can be bewildering, for example, in the considered example [mol - 1 m 3] for K s and [Pa - 1] for K r , but there is nothing wrong with that. If the sums of the stoichiometric coefficients of products and starting materials are equal, the equilibrium constant will be dimensionless.
Sam showed up to give me the news about eleven o'clock.
They're going to arrest Jason as soon as he wakes up, Sookie. It looks like it will happen very soon.
Sam didn't tell me how he knew that, and I didn't ask.
I looked at him and tears streamed down my face. Any other day, I would probably think about how bad I look when I cry. But today I didn't care about looks at all. I was all a bundle of nerves: afraid for Jason, sad about Amy Barley, angry at the police for their ridiculous mistake, but at the bottom of all these feelings lay a longing for Bill.
They believe Amy Barley resisted and he got drunk after he killed her.
Thank you, Sam, for warning me, - my own voice sounded from somewhere far away. - Go to work.
When Sam realized that I really was better off alone, and left, I called the help desk and got the number for Blood on the Block. I dialed the numbers, feeling that I was doing something wrong, but I could not understand why.
Krooooo… in the block,” a deep voice proclaimed dramatically. - Your coffin is in foreign lands!
Oh my God!
Good morning. You're concerned about Sookie Stackhouse at Bon Temps, I said politely. - I need to relay information for Bill Compton. He is your guest.
Fang or human?
Uh-uh… fang.
Just a minute please.
Your message ma'am.
This got me thinking.
Please inform Mr. Compton that my brother has been arrested, and I would greatly appreciate it if he could return home as soon as his business was done.
I wrote everything down, - the scratching of a pen on paper was heard in the tube. - Once again your name?
Stackhouse. Sookie Stackhouse.
Okay, miss. I'll make sure he gets your message.
This was the only action I could take until I realized that it would have been better to call Sid Mutt Lancaster. He tried to pretend that he was very upset by the news that Jason was going to be arrested. And he promised to go to the hospital as soon as he was released in court, and immediately inform me of the results.
I went to the hospital, hoping they would let me sit with Jason until he recovered. But they didn't let me. I asked if he had regained consciousness, but they didn't tell me anything. At the far end of the hall, I spotted Andy Bellefleur, but he turned and walked away.
Cursed coward.
I returned home because I couldn't think of what else to do. I remembered that I had a day off today, and was glad of this, although the work did not bother me too much. It occurred to me that I no longer attach due importance to the work, having become much more stable since my grandmother died.
But this situation had its limit. We buried the grandmother, her killer must be arrested, and life goes on. If the police seriously believe that Jason killed not only all these women, but also the grandmother, then the world was such a disgusting place that I did not want to live in it anymore.
As I sat and stared ahead of me, in this endless day, I realized that my naivety was the reason for Jason's arrest. If I had dragged it into Sam's trailer, cleaned it all out, and hidden the cassette until I figured out what was on it and called an ambulance... Sam thought about all these implications as he looked at me with such doubt. To some extent Arlena's arrival did not give me time to decide.
I thought that as soon as everything became known, the phone would ring incessantly.
But no one called.
They had nothing to say to me.
About half-past four Sid Mutt Lancaster appeared. He informed me without any preparation:
They arrested him. Murder in the first degree.
I closed my eyes. When I opened them, Sid looked at me with a penetrating expression on his good-natured face. Old-fashioned black-rimmed glasses enlarged his brown eyes, and his jaw and pointed nose made him look like a bloodhound.
And what does he say? I asked.
He said he was with Amy last night.
I sighed.
They went to bed together, and he had known her before. He said he had not seen Amy for a long time. The last time they were together, she was jealous of the many women he dated. So he was surprised when she approached him that evening at Good Days. Jason said that Amy was generally acting weird, like she had something on her agenda that he didn't know about. He remembers how they made love, remembers how they drank together in bed after that, but nothing more, until the moment he wakes up in the hospital.
He was framed, - I said decisively, thinking that it all looked like a low-profile television detective.
Of course.” Sid Mutt's eyes were as calm and as sure as if he himself had been at Amy Barley's last night.
Oh my God, why, maybe he was there!
Listen, Sid Mutt, - I leaned in, and our eyes met. - Even if I can somehow be convinced that Jason killed Amy, Don and Maudet, then I will not believe in my life that he could raise a hand against his grandmother.
Good. - Sid Mutt was clearly ready for an open and honest conversation, his whole appearance spoke about this. “Miss Sookie, let's assume for a moment that Jason has something to do with these deaths. Then it's possible, at least that's what the police think, that your buddy Bill Compton killed your grandmother because she interfered with your relationship.
I pretended to try to treat this statement as something reasonable.
No, Sid Mutt, my grandmother liked Bill Compton and was glad we were dating him.
Before he put on his gambler's mask again, I could see the disbelief in the lawyer's eyes. He would not be happy at all if his daughter began dating a vampire. He couldn't imagine another reaction from a responsible parent. And he could not imagine how he would convince the jury that the grandmother was glad to meet her granddaughter with a person who cannot be called alive, and, in addition, a good hundred years older.
So thought Sid Mutt.
Have you met Bill? I asked. He was confused.
No, he admitted. - You know, Miss Sookie, I'm not a big fan of all these vampire games. It seems to me that we are pulling the bricks out of a wall that should be strong, which is designed to separate us from the so-called infected. I believe the Lord created this wall, and my section of the wall will remain standing.
The problem, Sid Mutt, is that I was made to sit on top of that wall. “After having kept silent about my “gift” all my life, now I was ready to blurt it out in the face of anyone if it could help Jason.
Well, said Sid Mutt bravely, moving his glasses across the bridge of his nose. - I am sure that the Lord has created a problem for you that I have heard about, not without a reason. And you must learn to use it to the greater glory of the Lord.
No one has ever imagined it this way. It was worth thinking about at your leisure.
I'm afraid I've made us digress from the main topic of the conversation, and your time, as far as I know, is precious. - I concentrated. - I want Jason to be released on bail. After all, as far as I understand, in Amy's case against him there is only circumstantial evidence.
He admitted that he was with the victim just before the murder. The videotape, as one of the police officers very clearly hinted to me, confirms that your brother had sex with her. The time and date on the tape indicates that the recording was made hours, if not minutes, before her death.
Jason's damn bed preferences!
Jason never drinks much. And in the truck, he reeked of alcohol. I think it was just spilled on Jason. Probably, this will show the examination. Perhaps Amy slipped some kind of drug into his drink.
Why would she do this?
Because, like so many other women, she was crazy about Jason. My brother is able to charm anyone. No, I won't use a euphemism.
Sid Mutt was surprised that I knew such a word.
He could go to bed with anyone he wanted. According to most guys - heavenly life. - Fatigue fell on me like a fog. And now he's in jail.
Do you think the other man is to blame? What did he set him up for?
Yes, that's exactly what I think. I leaned forward, trying to convince the skeptical lawyer with the strength of my faith. - Someone envied him. Someone knew his schedule, killing women on the days Jason wasn't working. Someone knew that Jason was making love to all these girls. Someone also knew that he liked to make videos.
It could be almost anyone, - Jason's lawyer reasonably noted.
Yes, I replied sadly. - Even if Jason was smart enough to keep silent about who exactly he met, then it was enough for anyone to pay attention to who he left the bar with. Observant enough, yes, maybe you should have asked him about the notes while at his house. - My brother may have been deprived of some moral principles, but still I don’t think that he showed these records to just anyone. Yet he could tell anyone that he was going to make such records. - So this man, whoever he was, somehow communicated with Amy, knew that she was pining for Jason. Maybe he told her he wanted to play a joke on Jason or something.
Your brother has never been under arrest before,” Sid Mutt said.
No. - Although, if you listen to Jason, he came close to it a couple of times.
No previous offenses, positive citizen, permanent job. I'll probably be able to get him out on bail. But if he hides, you lose everything.
It never crossed my mind that Jason might run away on bail. I didn't know anything about how it was done, what my actions would be, but I really wanted to get Jason out of jail. The fact that he would be in jail before the official trial somehow made him look more guilty.
If you find out anything, let me know what I need to do, I asked. - Can I meet him before then?
He wouldn't want that, Sid Mutt told me. For some reason, this message caused me terrible pain.
Why? I asked, trying my hardest not to cry.
He's ashamed," the lawyer said.
The thought that Jason might be ashamed struck me.
Well, I said, suddenly tired of this useless meeting, call me when I can do something.
Sid Mutt nodded, his jaw twitching slightly as he moved. My presence embarrassed him, and he was glad that he was leaving.
The lawyer retired in his pickup truck, cowboy hat pulled over his head while he was still in sight.
When it got completely dark, I went out to check on Bubba. He was sitting under a holly, with a pile of blood bottles in front of him, empty on one side, full on the other.
I had a flashlight, I knew that Bubba was somewhere nearby, but it still shocked me to see him in the beam of light. I shook my head. Something had really gone wrong with Bubba when he came to, there was no doubt about it. Bubba's eyes were completely insane.
Hi honey! he said, his southern accent thick as syrup. - How are you doing? Will you keep me company?
I just wanted to make sure you're comfortable," I replied.
You know, there are a lot of better places than this, but since you're Bill's girlfriend, there's no need to talk about them.
That's right, I said firmly.
Are there any cats nearby? I'm tired of this nonsense in bottles!
No. But I'm sure Bill will be back soon and you can go home.
And I headed home, feeling too uncomfortable in Bubba's presence to continue the conversation, if you could even call it that. I wonder what Bubba thought about during those long nights of watching, did he remember his past?
And how is your dog? he called to me.
Gone home,” I said over my shoulder.
Too bad, Bubba said to himself, so quietly I could barely hear him.
I made my bed, watched TV, ate ice cream, and even bothered to grate some chocolate for dusting. None of the usual little joys worked this evening. My brother was in jail, my boyfriend was in New Orleans, my grandmother was dead, and some bastard killed my cat. I was lonely and sorry for myself.
But sometimes you have to worry about it.
Bill didn't answer my call.
It only added fuel to the fire of my suffering. He must have met some hospitable witch in New Orleans, or the fang-fist of those who curl up every night at Blood on the Block, hoping for a date with a vampire.
If I were an alcoholic, I would get drunk. If I had been more easygoing, I would have called the handsome G.B. du Rhone and slept with him. But I am far from such drama, so I limited myself to ice cream and old movies on TV. By a strange coincidence, Blue Hawaii was shown there.
I went to bed around midnight.
I was awakened by a scream outside my bedroom window. Sitting up in bed, I heard a crash and a thud, and finally a voice that clearly belonged to Bubba called out:
Get out, honey!
Without hearing anything else for a couple of minutes, I threw on my bathrobe and walked to the front door. The yard, flooded with the light of signal lamps, was empty. I saw movement to the left, and poking my head out the door I saw Bubba returning to his ambush.
What happened? I called softly.
Bubba changed direction and walked towards the threshold.
Clearly some son of a bitch, pardon the expression, was hanging around the house,” Bubba informed me. His brown eyes shone and he looked more like his old self. “I heard him before he got here, and I was hoping to intercept him. But he rushed to the road through the forest, and there he had a truck.
Have you had time to look at it?
Not enough to describe,” Bubba admitted with a guilty smile. - He arrived in a pickup truck, but I didn’t even understand what color it was. Dark.
And yet you saved me, - I said, hoping that sincere gratitude would sound in my voice. I felt a wave of gratitude towards Bill, who organized my security. Even Bubba has become nicer to me than he used to be. - Thank you, Bubba.
No need to thank me, Bubba answered me gallantly. At that moment, he straightened up, tilted his head back a little, a smile wandered on his face ... Then was he and I were about to say his name when Bill's warning flashed into my mind and I remained silent.
The next day, Jason was released on bail.
It cost me a fortune. I signed what Sid Mutt pointed out to me, even though Jason's house, truck, and fishing boat were most of the collateral. If Jason had ever been arrested before, even for some nonsense, I don’t think they would have agreed to let him go.
I was standing on the stairs of the courthouse, dressed in a creepy sea-green formal suit that almost melted me in the late morning heat. Sweat ran down my face, dripping down my lips, making me want to jump into the shower immediately. Jason stopped in front of me. I wasn't sure if he would speak to me. He looked much older. Now he had a real misfortune behind him, from which you can’t dismiss it like that, which you can’t wait out like grief.
I won't talk to you about this," he said so quietly that I could barely hear him. - You know I didn't do it. I have never been a supporter of violence, except for a couple of fights over women.
I touched his shoulder and my hand dropped when he didn't react.
I never thought it was you. And I never will. I'm sorry I was such an idiot and called 911 yesterday. If I'd known straight away it wasn't your blood, I'd have moved you to Sam's trailer, cleaned it up and put away the tape. I was just terrified that it was your blood. I felt my eyes fill with tears. But now was not the time to cry, so I pulled myself together and my face tightened. Jason's mind was a hodgepodge, a mental pigsty. From the infernal mix floated regret, shame at having made his sexual habits public, guilt at not regretting Amy's death enough, horror that someone in town might think he'd killed his grandmother while he was waiting for his sister.
We'll get through," I said helplessly.
We'll get through, - he repeated, trying to give his voice strength and confidence. But it seemed to me that it would be a long time before Jason's confidence, that feeling that made him irresistible, returned to his master, filled his speech and lit up his face.
Or maybe it will never happen again.
Here, at the court, we parted. We had nothing to say.
I sat in the bar all day, peering at the men who came in, trying to read their minds. None of them thought about how he killed four women and how he managed to escape justice until now. At lunchtime, Hoyt and René came in through the door, but immediately came out again when they saw me in the bar. Perhaps my presence confused them.
Finally, Sam made me leave. He said that I was so terrifying that I scared off all the visitors who could give me any information.
I walked out the door and into the sun. Sunset was approaching. I thought of Bubba, of Bill, of all the creatures that wake up from their dead sleep to walk the surface of the earth.
I stopped by Grabbit Quick to buy some milk for breakfast. The new attendant turned out to be a pimply youth with a large Adam's apple. He stared at me as if he wanted to imprint the image of the killer's sister in his mind forever. I realized that he couldn't wait until I left to call his girlfriend. He tried to see the teeth marks on my neck. He also wished he could find someone to tell him how vampires do it.
And this is the garbage I had to hear day after day. No matter how focused I was on the other side, no matter how thoroughly I held my guard and how broadly I smiled, it still seeped through.
I got home when it was getting dark. After removing the milk and taking off my suit, I put on shorts and a black T-shirt and tried to come up with an activity for tonight. I couldn't calm down enough to settle down to read. I still had to go to the library and change the books, which under the current circumstances was too much of an ordeal. There was nothing good on TV in the evening. I thought about watching The Brave Heart again: Mel Gibson in a kilt is superbly uplifting. But too much blood was spilled on my mood today in this film. I couldn't stand the scene where this girl's throat is slit, even if I know the moment when I need to close my eyes.
I made my way to the bathroom to wash off my sweaty makeup when, over the sound of running water, I thought I heard a howl coming from outside.
I turned off the water and froze, listening intently. What?.. Water dripped from his face onto his T-shirt.
Not a sound. Complete silence.
I made my way to the front door, which was closest to Bubba's vantage point.
I opened the door and yelled:
No answer.
I tried again.
It seemed to me that even the toads and grasshoppers held their breath. The night was so quiet that anything could be in the silence. Something was trying to emerge from there, out of the darkness.
I tried to think, but my heart was beating so fast that it was hard for me to concentrate.
First, call the police.
And then it turned out that it was impossible. The phone was silent.
So I could either sit in the house, waiting for what would fall on me, or run into the forest.
The choice was not easy. I bit my lower lip as I walked around the house and turned off the lights, trying to work out a course of action. The house provided some protection: castles, walls, nooks and crannies. But I knew that if someone intended to break into the house, he could do it, and then I would be trapped.
OK. How do I get out without being seen? For starters, I turned off the outdoor lights as well. The back door was closer to the forest, so this choice seemed to me more successful. I knew the local forests well and could wait there until light. Maybe I could get into Bill's house. The phone must have worked there, and I had the key.
Or you could try to get to the car and start it. But it connected me to a certain place for a few seconds.
No, the forest seemed to me the best option.
In one of the pockets I found Bill's key and Grandma's folding knife. Grandma kept it on the table in the living room and used it to open letters. In another pocket, I found a small flashlight. In a closet near the front door, my grandmother also kept an old gun. It had belonged to her father when he was little, and she used it to shoot snakes. Well, I had to shoot the snake. I hated this gun, hated the thought of having to use it, but now seemed like the right time.
But he wasn't there.
With difficulty believing myself, I searched the entire closet.
He was in my house!
But the house was not broken into.
Someone I invited. Who has been here? I tried to remember everyone as I walked to the back door, tying the bows on my T-shirts to avoid stepping on a dangling lace. Carelessly, almost with one hand, I tied my hair into a ponytail so that it would not fall on my face, pulling it off with an elastic band. But all this time I thought about the stolen gun.
Who visited me? Bill, Jason, Arlena, Renee, kids, Andy Bellefleur, Sam, Sid Mutt. I'm sure I left all of them at least for a few minutes, which could be enough to take the gun out of the house, and later re-store it.
Then I remembered the day of the funeral. Almost everyone I knew was in and out of the house when my grandmother died, and I wasn't sure if I had seen the gun since.
But it seemed unlikely to me that someone casually walked out of a crowded house with a gun on his shoulder. And if she had disappeared then, I think I would have already noticed her absence. Of this I was almost certain.
But now I should have put those thoughts aside and thought about what awaits me in the darkness.
I opened the back door and stepped out of the house, keeping as close to the ground as possible, closing the door softly behind me. I decided not to go down the stairs, but crouching on the threshold, I found the ground with one foot. Then she shifted her weight onto her and lowered her other leg. And leaned over again. It reminded me so much of Jason and I playing hide-and-seek when we were kids.
I wanted to believe that I wasn't playing hide-and-seek with him now.
I used my grandmother's flower tub as my first cover, then moved to her car, which became my second cover. I looked at the sky. The moon was young, the night was clear and the sky was full of stars. The air was heavy with moisture, and it was still hot. My hands were covered in sweat within minutes.
The next step: from the car to the mimosa tree.
This time, things didn't go so smoothly. I tripped on a stump and hurt myself badly. I had to bite my lip to keep from screaming. The pain shot through my entire leg, I realized that the clumsy stump had rather severely torn my thigh. And what did it cost me to go out and cut down this damned stump? Jason's grandmother asked about this, but he never had time.
I heard and felt movement. With a mental curse, I got up and headed for the trees. Someone was making his way along the edge of the forest to my right and moving towards me. But I knew what to do, and with a force that amazed me myself, I grabbed the lower branch of the tree, which we loved to climb in childhood, and pulled myself up. If I am destined to live to see tomorrow, all my muscles will hurt severely, but the game was worth the candle. I balanced on a branch, trying to hold my breath, although what I wanted most was to moan and whine.
Ah, if only it were all a dream. But no: no doubt it was I, Sookie Stackhouse, the waitress and telepath, sitting on a branch in the middle of the forest in the middle of the night, armed only with a penknife.
Traffic right below me. A man slipped out of the forest. A long cord dangled from his arm. Oh my God! Although the moon was almost up, the man's head stubbornly remained in the shadows, and I couldn't figure out who it was. He passed under a tree without noticing me.
When he was out of sight, I dared to inhale. As quietly as possible, I climbed down from the tree and made my way through the woods to the road. The road will take some time, but maybe I can stop a car. Then it occurred to me how rarely this road is used. Perhaps it would have been better to try and get through the graveyard to Bill's house. I thought of the cemetery at night, of the killer looking for me, and I shuddered.
But it was completely pointless to be scared even more. I needed to focus on what was happening here and now. I moved very slowly, carefully examining the places where I put my feet. If I fall here, I'll make a noise and he'll be here in no time.
About ten yards southeast of the tree I was hiding in, I came across a dead cat. There was a lacerated wound on her throat. In the moonlight, I couldn't even tell what color the cat was, but the dark spots around the small corpse were undeniably blood. Another five feet away I saw Bubba. He was either dead or unconscious. Quite difficult to define correctly when it comes to a vampire. But there was no stake sticking out of him, his head was still there, so I hoped he was only unconscious.
Someone must have given Bubba a drugged cat. Someone who knew that Bubba was protecting me and that he would not refuse cat blood.
I heard a crunch behind. In the blink of an eye, I slipped into the shade of a nearby tree. I was furious and terrified, and I wanted to know if I would make it through the night.
I didn't have a gun, but I had my own weapon. I closed my eyes and tried to reach his brain.
Plexus of dark, red, black. Hatred.
I shuddered. But it was inevitable, it was the only defense. I completely dropped the defense.
Images flooded into my head that made me sick, that horrified me. Don, who is asking someone to hit her and then sees that he has one of her stockings in his hands, he runs it through his fingers, preparing to tighten it around her neck. A fleeting vision of Maudet, naked and pleading. A woman I have never seen sits with her bare back towards me, covered in bruises and abrasions. And my grandmother - my grandmother - in our own kitchen, fiercely fighting for her life.
I was paralyzed with shock and horror. Whose thoughts were these? I saw Arlen's children playing on my living room floor, I saw myself, even though I didn't look like what I used to see in the mirror. There were huge holes in my neck, I was depraved, a meaningful grin played on my face, and I stroked my inner thighs invitingly.
I was in the brain of René Leinier. And that's how he saw me.
Rene was crazy.
Now I understood why I could never read his mind clearly. He kept them hidden, in a part of the brain where he could hide them, separating them from his consciousness.
Now he saw some shapes behind the tree, and they reminded him of the shape of a woman.
He saw me.
I rushed west to the cemetery. I could no longer listen to his thoughts as my head was busy running, how to get around obstacles in the form of trees, bushes, fallen trunks, puddles where rain accumulated. My strong legs kicked off, my arms lifted, my breath sounded like a bagpipe.
I escaped from the forest and ended up in a cemetery. The oldest part of the cemetery lay further north, towards Bill's house. There were better places to hide. I raced over the modern headstones, barely touching the ground, knowing that trying to hide was useless. I jumped over my grandmother's grave, the ground was still damp, there was no gravestone. Her killer was after me. I turned around to see how close he was, and in the moonlight I saw René's tousled head coming towards me.
I ran down the slope of the recess in which the cemetery was located, then began to climb the opposite one. Deciding that there was a sufficient number of tombstones and monuments between me and Rene, I dived behind a high granite column topped with a cross. There I froze, trying to merge with the cold stronghold of stone. I had to cover my mouth with my hand to muffle the sound with which my lungs tried to get enough oxygen. I calmed down enough to try to listen to Rene, but his thoughts were so confused that they could not be understood, except for the rage that seized him. Then came one clear vision.
Your sister, I screamed. - Is Cindy still alive?
Bitch! he yelled, and in that second I realized that the first woman to die was René's sister, who liked vampires, the one Arlene said René still visited from time to time. René killed Cindy, his waitress sister, while she was still wearing the pink and white uniform of a hospital cafeteria waitress. He strangled her with the straps of his apron. And had sex with her after she died. She's sunk so low she won't even mind her own brother, he thought, as far as he could think. Anyone who allowed a vampire to do this to her deserves to die. He hid her body out of shame. The others weren't his flesh and blood, and it was okay to let them lie down.
I was being sucked into René's sick brain like a piece of wood being sucked into a whirlpool, it shocked me. When I returned to my brain, it attacked me. He hit me in the face with all his might and expected me to fall. The blow broke my nose and caused such terrible pain that I almost passed out, but resisted. I hit back. Lack of experience rendered my strike ineffective. I just slapped him in the ribs, he grunted, and the next second he hit me again.
His fist broke my collarbone. But I stayed on my feet.
He didn't know how strong I was. By the light of the moon, I could see how surprised he was that I was trying to resist, and I mentally thanked the vampire blood that was in me. I thought of my brave grandmother and pounced on him, grabbed his ears and tried to bang his head against a granite column. His hands tried to grab mine and pull them back to loosen his grip. Finally, he succeeded, but I could see from his eyes that he was surprised and now on the alert. I tried to throw him to my knees, but he got ahead of me, twisting to avoid me. While I lost my balance, he pushed me, and I crashed to the ground.
Then he saddled me. But during our fight, he lost his lace, and holding my neck with one hand, he tried to find his chosen weapon with the other. My right hand was nailed, but the left was free, and she beat and scratched him. He had to ignore it, had to look for his string, which was part of the ritual. My hand stumbled upon a familiar object.
René, who was in work clothes, still wore a knife on his belt. With a jerk, I unfastened the scabbard and drew the knife from it. While he had time to think: “I should have taken it off,” I plunged the knife into his side, at an angle, then pulled it out.
Then he screamed.
He got to his feet, writhing, trying to press both hands on the bleeding wound.
Lord Jesus! Woman, what have you done? Oh God, how it hurts! Rene shouted.
It was strong.
Now he was afraid, he was afraid that he would be discovered, putting an end to his games, his revenge.
Girls like you deserve to die,” he growled. - I can feel you in my head, freak!
Who is the freak here? I hissed. - Take it easy, you bastard.
I didn't even know what I had in me. I stood crouched by the tombstone, my hand clutching at the bloodied knife, waiting for it to pounce on me again.
He moved in circles, staggering, and I watched with a stone face. I opened my brain to his sense of impending death. I was about to stab him again when he collapsed to the ground. After making sure he wasn't moving, I went to Bill's house. I didn't run, trying to convince myself that I just couldn't run, but I wasn't sure that was the point. I kept seeing my grandmother, forever imprinted in Renee's memory, fighting for life in her own home.
I pulled Bill's key out of my pocket, almost surprised it was still there.
Somehow I managed to turn it around, stumble into a large living room, reach the telephone. My fingers managed to find the buttons, determine which one was a nine and which one was a one. I pressed them hard enough that the buttons beeped, and then, without warning, I passed out.
I realized that I was in the hospital. I was surrounded by the clean smell of hospital sheets.
The next thing I realized was pain all over my body.
Someone was with me in the room. With some effort I managed to open my eyes.
Andy Bellefleur. His square face was even more haggard than when I had last seen him.
Can you hear me? - he asked.
I nodded. The movement was weak, but it echoed with a wave of pain in his head.
We detained him,” he said, and began to tell something further, but I fell asleep.
I woke up again in the afternoon, this time more animated.
Someone was in the room.
Kevin rose from a chair in the corner of the room, rolling up a crossword magazine and stuffing it into the pocket of his uniform.
Where is Kenya? I whispered.
He suddenly chuckled.
She sat here for a couple of hours,” he explained. - He'll be back soon. I sent her for dinner.
His thin face and body were a token of approval.
I don't feel strong, I managed to say.
You're just hurt," he told me, as if I didn't know it.
We found him in a graveyard,” Kevin told me. - You beat him badly. He was conscious and told us he tried to kill you.
He was really upset that he didn't finish the job. I still can't believe it was like that, but he was kind of hurt and kind of scared when we got to him. He told us it was all your fault because you didn't want to just lay down and die. He thought it was genetics because your grandmother…” Here Kevin trailed off, deciding he was stepping into an area that was too painful.
She fought too,” I whispered.
At that moment, Kenya entered, massive, impassive, holding a cup of steaming coffee.
She woke up, - said Kevin, beaming at the sight of his partner.
Okay, Kenya wasn't that excited about this event. - She said what happened? Maybe you should call Andy?
Yes, he asked for it. But he only slept for four hours.
He said to call.
Kevin shrugged and went to the phone next to the bed. I dozed off as he spoke, but through my slumber I could hear him and Kenya purring as they waited. He talked about his hunting dogs. Kenya, I understand, was listening.
Andy came in, I felt his thoughts, his mindset. His massive presence filled the room. When he bent down to look at me, I opened my eyes. We exchanged a long look.
Two pairs of legs retired into the hall.
He's still alive," Andy said sharply. And he won't stop talking.
I made a short movement of my head, which was supposed to indicate a nod.
He said it started because of his sister who was dating a vampire. Apparently, she had lost so much blood that Rene was convinced that she herself would turn into a vampire if he did not intervene. Once, being with her, he gave her an ultimatum. She refused, saying that she would not give up her beloved. She was just tying her apron, getting ready for work while they argued. He tore it off, strangled her, and… something else.
Andy obviously didn't like it.
I know, I whispered.
It seems,” Andy continued, “for some reason he decided that all his monstrous actions were justified by his own conviction that anyone in the same position as his sister deserved to die. In fact, the crimes here are very similar to the two murders in Shreveport, which have not yet been solved. We hope that Rene will tell us about it while he recovers. If he can.
I felt my lips tighten in terrible sympathy for all these unfortunate women.
Can you tell what happened to you? Andy asked quietly. - Speak slowly, in a whisper. You have bruises all over your neck.
Thank you very much, I figured this out myself. I murmured a brief account of the evening's events, trying not to miss anything. After asking my permission, Andy turned on a small voice recorder. He placed it on the pillow next to me after I allowed it, so the whole story was written down.
Is Mr Compton still out of town? he asked after I finished the story.
New Orleans,” I whispered, unable to speak anymore.
We'll look for the gun at René's house, since it's known who owns it. This would be a good confirmation.
A smiling girl in white entered the room. Looking me in the face, she asked Andy to come at another time.
He nodded to me, awkwardly stroked my hand, and left, giving the doctor a last look of admiration. She was quite admirable, but she had a wedding ring on her finger, so Andy was late again.
She decided that he was too serious and gloomy.
I didn't want to hear it. But I didn't have the strength to defend myself.
Miss Stackhouse, how are you feeling? the young woman asked a little too loudly. She was a slender brunette with large brown eyes and full lips.
Disgusting, I whispered.
I can imagine,” she said, nodding repeatedly as she looked me over. In fact, she could hardly imagine such a thing. I'm willing to bet she's never been beaten up in a graveyard by a serial killer.
You lost your grandmother recently, didn't you? she asked with participation. I nodded, moving my head a fraction of an inch.
My husband died about six months ago, she said. - I know what grief is. It's not easy being brave, is it?
Well, well, well. I let my expression become interrogative.
He had cancer, she explained. I tried to express my condolences without moving, but it proved impossible.
Well," she said, straightening up, returning to her quick manner. “Miss Stackhouse, you will certainly live. Your collarbone, two ribs and your nose are broken.
Shepherd of the Jews! No wonder I felt so bad.
Your face and neck have been badly beaten. Undoubtedly, you feel like your throat hurts.
I tried to imagine what I look like. Thank God I didn't have a pocket mirror.
You also have many bruises and abrasions on your arms and legs. She smiled. - But the stomach and feet are in perfect order.
Ha-ha-ha. Very funny.
I've prescribed painkillers for you, so if you feel unwell, call the nurse.
A visitor stuck his head in the door behind her. She turned around, blocking my view, and asked:
Is this Sookie's room?
Yes, I just finished my inspection. You can enter. - The doctor (judging by the badge, her name was Sonntag) looked at me questioningly to get my permission, and I managed to say:
Of course.
G.B. du Rhone floated up to my bed, looking like a picture from the cover of a romance novel. His brownish-yellow hair gleamed under the fluorescent lights, his eyes were almost the same color, and his sleeveless shirt exposed muscles that looked like they were carved with a chisel. He looked at me, and Dr. Sonntag looked at him.
Hey, Sookie, are you all right? he asked, gently touching his finger to my cheek. He kissed me on the forehead, choosing a place without bruising.
Thanks, I whispered. - You'll be fine soon. Meet my doctor.
G.B. drew attention to Dr. Sonntag, who almost stood on tiptoe to introduce herself.
Doctors have never been so charming before, - said G.B. simply and sincerely.
Have you been to a doctor since you were a child? Dr. Sonntag was surprised.
I never get sick, he smiled. - Healthy as a bull.
Well, the mind is almost the same. Although, perhaps, Dr. Sonntag has enough mind for two.
But she couldn't think of a reason to stay. Although she cast a wistful glance over her shoulder as she left. JB leaned towards me and seriously asked:
Can I bring you something? Chew or something like that?
The thought of crackers brought tears to my eyes.
No thanks, I breathed. - The doctor is a widow.
You can change topics of conversation with G.B., he won't be too surprised.
O! - He was impressed. - Nice and lonely.
I raised my eyebrows meaningfully.
Do you think I should invite her? - G.B. was as thoughtful as it is possible for him to be. “Maybe it’s not a bad idea. - He smiled at me. - Bye you you're not going to date me, Sookie. You will always be number one for me. Just wave your finger and I'll come running.
What a nice guy! I didn't believe his devotion for a second, but he knew how to please a woman, even if she looked deadly bad. And I also felt disgusting. Where are those pain pills? I tried to smile at G.B.
You feels bad? - he asked. - I'll send you a nurse.
Excellent. And then it seemed to me that the call button was moving away and moving away when I tried to move my hand. He kissed me again before leaving and said:
I'll go get your doctor, Sookie. I'll ask her about your health.
My sister filled the drip with some substance, and I was already waiting for the pain to stop when the door opened again.
My brother entered. He stood by my bed for a long time and looked into my face. Finally he said gloomily:
I was talking to the doctor before she went with GB to the cafe. She told me what happened to you. - He moved away from me, walked around the room, returned. Looked at me again. - You look awful.
Thanks, I whispered.
Ah, yes. your throat. I forgot.
He patted me, thinking of nothing better.
Look sis, I should thank you, but I'm sorry you had to fight for me.
If I could, I would gladly hit him now.
Fight for him, damn it!
I am very grateful to you. I was an idiot, considering Rene a true friend.
He felt betrayed.
Then Arlene came in, so that life would not seem like honey at all.
She was completely lost. Her red hair was messed up, she was wearing no make-up, and her clothes were picked at random. I have never seen Arlena without her hair styled and bright makeup.
She looked at me - oh my God, when will I be able to endure this again - and for a second her face turned to stone, but when she looked at me carefully, the granite crumbled.
I was so mad at you, I didn't believe it, but now I look at you and... what has he done! Oh, Sookie, will you ever forgive me?
Oh God, how I wanted her to go away. I tried to impress it on Jason, and this time the transmission was successful because he put a hand on her shoulder and led her out of the room. By the time they reached the door, Arlene burst into tears.
I didn't know…" she repeated, hardly realizing what she was saying. - I just didn't know anything!
Hell, I didn't know either! Jason said darkly.
Trying to swallow the delicious green gelatin, I dozed off.
The biggest distraction of the day was trying to get to the bath more or less on my own. I sat in the chair for ten minutes, after which I was quite ready to go back to bed. On the way, I looked at myself in the mirror, which lay on a gurney, and regretted it.
I had a slight fever, I was trembling, my skin became extremely sensitive. The face turned blue-gray, and the nose swelled twice. The right eye was swollen and almost closed. I shuddered, and even that hurt me. My legs… oh no, I didn't even want to check what was wrong with them. I carefully lay down and began to dream that this day would finally end. Maybe in four days I will feel just great! Job. I wonder when I'll be back at work?
I was distracted by a soft knock on the door. Another damn visitor. This time, even a stranger to me. An elderly lady with blue hair and red-rimmed glasses wheeled in a cart. The lady was wearing a yellow blouse, which was supposed to be worn at work by representatives of a voluntary society for helping the hospital called "Sunny Ladies".
On the cart were flowers for the sick of our wing.
I bring you my very best wishes! the lady said cheerfully.
I smiled, but it seemed not entirely successful, as the lady's cheerfulness waned sharply.
This is for you,” she said, holding up a potted plant tied with a red ribbon. - Here's the card, honey. So, what else is there for us… - This time it was a bouquet of pink rosebuds, pink carnations and some white flowers. It also came with a card. After examining the cart again, the lady said: - Well, aren't you happy? Here's another one!
The focus of the third offering was a strange red flower, the like of which I had never seen in my life. He was surrounded by a host of other, more familiar colors. I looked doubtfully at the last bouquet. "Sunny Lady" handed me a card and to him.
After she left, smiling, I opened the small envelopes, remarking grimly that in a good mood it was a little easier to move.
The potted plant was from Sam "and all of Merlotte's co-workers," according to a card written by Sam. I touched the glossy leaves and wondered where I would put it when I got home. The bouquet was from Sid Mutt Lancaster and Elva Dean Lancaster. The arrangement with a rare red flower (it seemed to me that this flower looked almost obscene, like an intimate part of a female body) was undoubtedly the most interesting of the three. I opened the card curiously. There was only a signature: "Eric."
But that was enough for me. How does he know I'm in the hospital? Why is there no news from Bill?
After tasting delicious red gelatin for dinner, I stared at the TV for a couple of hours, since there was nothing to read anyway, if I could. The bruises bloomed every hour, I felt exhausted to the limit, although all day I only went to the bathroom, and walked around the room a couple of times. I turned off the TV and rolled over on my side. I fell asleep, and in my sleep the pain of my body turned into nightmares. I raced through the cemetery, fearing for my life, tripping over rocks, falling into open graves, bumping into people I knew lying in the ground: my father and mother, my grandmother, Maudette Pickens, Don Green, and even a childhood friend who died on the hunt. I was looking for a certain tombstone, if I can find it, I will be at home, free, safe. They will all return to their graves and leave me alone. I ran from one tombstone to another, putting my hand on each of them, hoping that it would turn out to be necessary. I cried.
Darling, you're safe, - there was a familiar calm voice.
Bill, I muttered. I turned my face to the stone that I had not yet touched. My fingers touched the inscription "William Erasmus Compton". I opened my eyes as if cold water had been doused on me. I had to take a deep breath, screaming out, a wave of pain running down my throat. I gulped air, the pain of coughing through all my broken bones completed my awakening. A hand slipped under my cheek, and the cool fingers created a wonderful sensation on the heated skin. I tried not to whine, but a sound still escaped through clenched teeth.
Turn towards the light, honey, Bill said, lightly and casually.
I slept with my back to the light that my sister left in the bathroom. Now I obediently turned on my back and looked at my vampire.
I'll kill him,” Bill hissed, with a simple assurance that made me wince.
There would be enough tension in the room to send a whole crowd of the faint hearted for tranquilizers.
Hello Bill, I croaked. - I'm also glad to see you. Where have you been? Thank you for answering my call.
It sobered him up. He blinked, and felt the effort with which he forced himself to calm down.
Sookie, he said. - I did not call, because I wanted to tell about everything myself. I could make out the expression on his face. If I had to take a photo, I would say he was proud of himself.
He paused and looked at me.
I'm not hurt, - obediently I croaked, holding out my hand to him. He kissed her, leaning over me so that a slight shiver ran through my body. And believe me, a slight shiver is much more than what I was capable of on my own.
Tell me what happened to you? he asked.
Then lean towards me so that I speak in a whisper. Otherwise it hurts me.
He pulled a chair up to the bed, lowered the bed rail, and rested his chin on his crossed arms. His face was four inches from mine.
Your nose is broken, he said. I rolled my eyes.
I'm glad you noticed it, I whispered. - I'll tell the doctor when she comes.
He narrowed his eyes.
Stop trying to confuse me.
OK. Broken nose, two ribs and collarbone.
But Bill wanted to examine me himself, so he pulled the sheet off me. I completely petrified. Why, I was wearing a terrible hospital nightgown, I wasn't washed well enough, my face was a mess of colors, and my hair wasn't combed.
I want to take you home,” he declared, running his hands over me and carefully examining every cut and blow. Vampire Therapist.
I waved my hand, asking him to lean towards me.
No, I breathed, pointing to the IV. He looked at her suspiciously, although he certainly knew what it was.
I can turn it off, he said.
I shook my head.
Don't you want me to take care of you?
I let out an exasperated breath, hurting myself a lot.
Then she made a gesture with her hand that I was writing, and Bill searched the nightstands and found a notebook. Oddly enough, he had a pen. I wrote: "They will let me out of the hospital tomorrow if the temperature does not rise."
Who will take you home? - he asked. He stood by the bed again and looked at me with disapproval, like a teacher at a hopelessly stupid student.
"I'll ask them to call Jason or Charles Touten," I wrote. If things had been different, I would have automatically written Arlen's name.
I'll be there when it gets dark, he said.
I looked into his pale face, the pure whites of his eyes almost shining in the dimness of the room.
I'll heal you, he offered. Let me give you my blood.
I remembered how brightened my hair, remembered that I was already almost twice as strong as before. I shook my head.
Why not? he asked, as if offering me a sip of water when I was thirsty and I refused. I figured I might have offended him with that.
Taking his hand, I brought it to my lips and kissed it gently. Then they brought it to the cheek that was less affected.
“People notice how I change,” I wrote after a moment. “And I notice that I am changing.”
He bowed his head for a moment and then looked at me sadly.
"Do you know what happened?" - I wrote.
Bubba told me something,” he said, and his face turned frightening as he spoke of the crazy vampire. Sam told me the rest, then I went to the police station and read their reports.
"Andy allowed it?" - I wrote.
No one knew I was there,” he replied nonchalantly.
I tried to imagine it, and goosebumps crawled up my skin.
I looked at him disapprovingly.
“Tell me what happened in New Orleans,” I wrote. I wanted to sleep again.
Then you will have to tell about our organization, - he said with doubt in his voice.
Wow, scary vampire secrets! I screeched.
It was his turn to look at me disapprovingly.
We observe some kind of organization,” he told me. - And I was trying to figure out how to keep us safe from Eric. I involuntarily glanced at the red flower.
I knew that if I took an official position, like Eric, it would become much more difficult for him to interfere in our personal lives.
I looked up with encouragement, at least I tried.
I attended a regional meeting and although I had never been politically active before, I submitted a petition. And won through increased lobbying.
It was absolutely amazing. Bill is a trade unionist! I wonder what the enhanced lobbying is. Did that mean killing all competitors? Or bribing voters with a bottle of Rh-positive type A blood?
"And what will your job be?" - I slowly brought out, imagining Bill during the meeting. And she tried to look proud, which was what Bill wanted.
I'm an investigator for the Fifth District," he said. - What does it mean, I'll tell you at home. I don't want to bore you.
I nodded and smiled at him. I really hoped that it would not occur to him to ask where all these flowers were from. I wonder if I should write Eric a thank you note. For some reason, everything got mixed up in my head. It's probably because of the painkillers.
I gestured for Bill to come closer. He did so, his face on the bed next to mine.
Do not wane Rene, - I whispered.
He became colder, colder, icier.
Maybe I've already done it. He's in intensive care. But if he survives, the killings are already enough. Let the law decide everything. I don't want any more witch hunts because of you. I want rest. It became very difficult for me to speak. I took his hand in mine and brought it back to his cheek, which was less bruised. All of a sudden, how much I've missed Bill, my chest tightened, and I held out my arms to him. He carefully sat down on the edge of the bed and leaned towards me. Then, very, very gently, he brought his hands under me and lifted me up, slowly, slowly, giving me a chance to tell if it hurt.
I won't kill him, he finally said in my ear.
Darling, I breathed, knowing that his sharp ears would pick up my words. - I missed. I heard him sigh, his hands gripping me a little tighter and sliding gently down my back.
How soon can you get better without my help? - he asked.
I'll try to hurry up," I whispered. - I think I'll surprise the doctors.
A collie ran down the corridor, peered through the open door, said "R-r-waff" and left. Surprised, Bill turned and looked down the corridor. Well, yes, the moon was full - I could see it through the window. But I also saw something else. A white face emerged from the darkness and floated between me and the moon. It was beautiful, framed by long golden hair. The vampire Erik smiled at me and disappeared from view. He flew.
Everything will be back to normal soon,” Bill said, gently laying me down to turn off the light in the bathroom. He glowed in the dark.
Yes, I whispered. - That's right. 0, then
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