16 Chemical Equilibrium

Reactions seldom go complete such that one of the reactants is exhausted as we have discussed in stoichiometry and limiting reagent. Instead, they are mostly reversible. For example, CO (g) + 3 H2 (g) CH4 (g) + H2O (g) The two-head arrow (or equal signs =) indicates that the reaction goes both ways. Similarly, N2O4 (colorless gas) 2 NO2 (brown gas) (show a film) When the forward and reverse reaction rates are equal, the system is said to be at equilibrium.
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1

The NASA Computer program CEA (Chemical Equilibrium with Applications) calculates chemical equilibrium compositions and properties of complex mixtures. Applications include assigned thermodynamic states, theoretical rocket performance, ChapmanJouguet detonations, and shock-tube parameters for incident and reflected shocks.

16 Chemical Equilibrium

1 mol CH4 2 mol S2 T = 1000 K P = 1.5 atm Countours show G/RT Equilibrium occur at minimum G/RT

16 Chemical Equilibrium

A System
Scientific experiments usually investigate a system, which is isolated from its environment or surrounding. The system can be a nucleus, an atom, a molecule, a plant, an animal, an experimental setup, the Earth, the solar system, the galaxy, or the universe. Matter and energy can be transferred into or out of a system.
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The environment or
The open or closed system The surrounding

Chemical Equilibrium

a dynamic process

Chemical equilibrium is a state of a system when reaction rates in both directions are equal. Changes continue at the molecular level, but the macroscopic properties stay the same. Equilibrium is a dynamic rather than static process. Heat is energy flowing from a high temperature object to a low temperature object. Equilibrium is reached when the temperatures are the same. Molecules still exchange kinetic energies during collision. Water flows from a high potential-energy place to a low potential-energy place. When potential energies are the same, water stops flowing. Watermolecule diffusion continues.

16 Chemical Equilibrium

Some Typical Equilibria

Macroscopic properties such as vapor pressure, solubility, distribution of a substance in two immiscible liquids are typical equilibria. Vapor pressure of a liquid is the pressure of the vapor in equilibrium with a liquid. It is a function of temperature. Solubility, amount in solution in equilibrium with solid, depends on the substance and the solvent, often also on temperature. Distribution (or equilibrium) coefficients of a substance in immiscible liquids are useful guides for the separation of mixtures into components.

16 Chemical Equilibrium

The reaction quotients

For any chemical reaction in a system, aA+ b B c C + d D we can always write a quotient, [C]c [D]d Q = [A]a [B]b for example, [NO2]2 Q = [N2O4] Know the definition of Q. Text: 16-5 defines Q & 16-1 defines K.

(Q is reaction quotient)

for N2O4 2 NO2

16 Chemical Equilibrium

Expressions for reaction quotients

For the ionization of an acid, H2SO4 = 2 H+ + SO42what is the reaction quotient expression? Hint: The reaction quotient is

[H+]2 [SO42-] = Q [H2SO4]

If M is used for the concentrations, what are the units for Q?

16 Chemical Equilibrium

More expressions for reaction quotients

2 H2 + O2 2 H2O [H2]2 [O2] 1 Q r = = [H2O]2 Q 4 H2 + 2 O2 4 H2O [H2O]2 Q = [H2]2 [O2] 2 H2O 2 H2 + O2 [H2O]4 Q2 = = Q 2 [H2]4 [O2]2

All relations are due to definitions. See 16-3

Q=Q2 Note the relationships

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Equilibrium constant - mass action law

When a chemical reaction in a closed system is at equilibrium, the reaction quotient is defined as the equilibrium constant, K, which depends on T. For a chemical reaction in a closed system, aA+ b B c C + d D then [C]c [D]d Q = = K (at equilibrium) [A]a [B]b Units of K depends on units of [ ]s, M(a+b-c-d) if M is used.

If Q < K, the reaction goes forward if Q = K, the system is at equilibrium if Q > K, the reaction goes backward See 16-5 & 16-3

| to increase [product] |the law of mass action | to decrease [product]

10

16 Chemical Equilibrium

Evaluating K
The equilibrium mixture is found to contain 0.07, 0.11, 0.03 and 0.03 moles of CO, H2, CH4 and H2O respectively for the reaction: CO (g) + 3 H2 (g) CH4 (g) + H2O (g) What is the equilibrium constant, K? Solution CO (g) + 3 H2 (g) CH4 (g) + H2O (g) start 0.07 0.11 0.03 0.03 (0.03) (0.03) K = = 9.7 (0.07) (0.11)3 What governs the quantitative relationship 16 Chemical Equilibrium among equilibrium mixtures?

11

Evaluate quantities
When 0.10 moles CO and 0.20 moles of H2 are placed in a 1-L vessel at temperature T and allowed to come to equilibrium. The mixture is found to contain 0.03 moles H2O for the reaction: CO (g) + 3 H2 (g) CH4 (g) + H2O (g) What is the equilibrium constant, K? Solution (note the strategy please) CO (g) + 3 H2 (g) CH4 (g) + H2O (g) start 0.10 0.20 0 0 change - x - 3x +x +x (x=0.03) eqlbm 0.1-x 0.2-3x 0.03 0.03 [] 0.07 0.11 0.03 0.03 K = (0.03) (0.03) / (0.07) (0.11)3 = 9.7
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Evaluate quantities
When 0.08 moles CO, 0.14 moles of H2, and 0.08 moles of CH4 are placed in a 1-L vessel at temperature T and allowed to come to equilibrium. The mixture is found to contain 0.01 moles H2O for the reaction: CO (g) + 3 H2 (g) CH4 (g) + H2O (g) What is the equilibrium constant, K? Solution (note the strategy please) CO (g) + 3 H2 (g) CH4 (g) + H2O (g) start 0.08 0.14 0.08 0 change - x - 3x 0.08+x +x (x=0.01) eqlbm 0.08-0.01 0.14-0.03 0.08+0.01 0.01 [] 0.07 0.11 0.09 0.01 K = (0.09) (0.01) / (0.07) (0.11)3 = 9.7
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13

Entropy
We all know that heat flow from a high-T object into a low-T object. This type of change can be described as due to increase of entropy. Entropy S is the amount of energy transferred, E, divided by T. E S = or TS = E T Entropy increases for spontaneous changes (reactions). Entropy is also associated with randomness of ordering. What causes change when no apparent energy is involved?
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Entropy calculation
A system consists 10.0 L of water at 300 K and 3.0 g of ice at 273 K. Heat of fusion of ice (molar mass 18) is 6 kJ/mol. What is the change in entropy when the system is at equilibrium. Solution: Since the amount of heat for melting the ice is 6 *(3/ 18) = 1.0 kJ too little to change the temperature of the entire system appreciably from 300 K. Thus the entropy change is 1/300 + 1/273 = 3.3e 4 kJ/K = 0.33 J/K (entropy unit)

What is the molar entropy for ice melting?

+6000 J mol1 / 273 K = 22 J mol 1 K 1 (entropy unit mol1)
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15

Josiah W. Gibbs
(1839-1903) New Haven, Connecticut, USA

First Doctorate (1863 Yale) in Engineering of U.S.A.

Studied in Europe, influenced by Kirchhoff & Helmholtz. 1871 Professor of mathematics and physics at Yale

Unassuming in manner, genial and kindly in his intercourse with his fellowmen, never showing impatience or irritation, devoid of personal ambition of the baser sort or of the slightest desire to exalt himself, he went far toward realizing the ideal of the unselfish, Christian gentleman. In the minds of those who knew him, the greatness of his intellectual achievements will never overshadow the beauty and dignity of his life. - Bumstead
lunar crater Gibbs
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16

Gibbs free energy, G or G

Following the definition of entropy S, Gibbs defined a function together with enthalpy of change, H.

G=HTS
or G = H T S

now called Gibbs free energy.

for differences of these quantities

Since H is negative and S is positive for spontaneous change, Gibbs free energy is negative for all spontaneous changes, and it unified enthalpy and entropy for changes. Gibbs free energy is the maximum amount of available energy in any change. Similar to Ho, Go is the Gibbs free energy at the standard T and P. What drives physical and chemical changes?
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17

Energy and equilibrium constant K

A quantity called Gibbs free energy, G, is defined as the maximum amount of energy from a chemical reaction for doing work. G is negative for spontaneous reaction G is positive for non-spontaneous reaction The G is related to the reaction quotient Q, G = Go + R T ln Q When a system is at equilibrium there is no available energy, G = Go + R T ln K = 0 Thus, Go = R T ln K, ln K = Go / R T K = exp ( Go / R T)
16 Chemical See 20-2 to 20-6 page 784-808 plse Equilibrium
18

More expressions for equilibrium constant

Note these relationships in light of ln K = Go / R T [H2O]2 K = [H2]2 [O2]

2 H2 + O2 2 H2O [H2]2 [O2] 1 K r = = [H2O] 2 K 4 H2 + 2 O2 4 H2O

2 H2O 2 H2 + O2
[H2O]4 K2 = = K 2 [H2]4 [O2]2 K2=K

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19

An Example
Hydrogen iodide, HI, decomposes, 2 HI H2 + I2

The amount of I2 can be determined from the intensity of the violet color of I2. When 4.00 mol of HI was placed in a 5.00-L vessel at 458oC, the equilibrium mixture was found to contain 0.442 mol I2. What is the value for K for the decomposition of HI at this temperature?

See 16-4 and 16-7 for this and the following examples.
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Analysis of Example
Hydrogen iodide, HI, decomposes, 2 HI H2 + I2

The amount of I2 can be determined from the intensity of the violet color of I2. When 4.00 mol of HI was placed in a 5.00-L vessel at 458oC, the equilibrium mixture was found to contain 0.442 mol I2. What is the value for K for the decomposition of HI at this temperature?
Analysis of the problem: [HI]0 = 4.0 mol / 5.00 L = 0.800 M [I2]equilibrium = 0.442 mol / 5.0 L = 0.0884 M Know your strategy
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Calculate Kc
Example 14.3 The equilibrium concentration of various species are given below their symbols, start change equlbm value

2 HI (g) = H2 (g) + 0.800 0 =? =? 0.800-2x x 0.6232 0.0884

I2 (g) 0 = 0.0884 M from experiment x 0.0884 M

0.0884*0.0884 Kc = = 0.0201 (0.6232)2 Skill: re-interpret question. Evaluate other quantities and K from known start conditions and experimental results

Evaluate Go

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22

Evaluate Kc
Compare with slide 41 At 300 K and 1 atm, an equilibrium mixture contains 70% NO2 by mass in a tube of NO2 and N2O4. Evaluate Kc for the reaction,

N2O4 = 2 NO2
The challenge (hint):

assume 100 g total mass (70 g of NO2 and 30 g N2O4) find amount in mole for each (1.522 mol NO2; 0.326 mol N2O4) find volume from pressure for all (45.49 L) find concentration from volume (0.0335 M NO2; 0.00717 M) evaluate Kc (equation dependent)

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23

Application of Kc
For N2O4 (g) = 2 NO2 (g) Kc = 4.20e-3 at 300 K, What are the equilibrium concentrations if 0.100 mol of N2O4 is placed in a 5.00-L flask?

Strategy: write down the equation figure out the initial condition assume the change to be x figure out the equilibrium concentration use the concentration-Kc relationship solve for x and then check the results.
4x2 + 0.0042 x 0.0000926 = 0 -0.00463 + {(4.63e-3)2 4*4*(-9.265e-5)} x = = 4.27e-3 2*4
16 Chemical Equilibrium

N2O4 (g) = 2 NO2 (g) 0.0200-x 2x (2x)2 = 4e-3 (K) 0.0200-x N2O4 (g) = 2 NO2 (g) 0.0157 8.54e-3 M
24

Evaluate equilibrium concentrations of all for the reaction condition as given in the start: (at T1) N2 (g) + 3 H2 (g) 2 NH3 (g) K = 1e-5 start 1.0 2.0 0 change - x - 3x +2x (= ?) eqlbm 1.0-x 2.0-3x 2x (2 x)2 = 1e-5 (1-x)(2.0-3x)3 4x2 = 1e-5 (1.0-x)(2.0-3x)3 x2 = 1e-5*1.0*2.03/4 = 2e-5 x = 4.5e-3 (justified)

Approximations
Results: [N2] = 0.995 M [H2] = 1.99 [NH3] = 9e-3 Checking

(2*4.5e-3)2 = 1e-5 0.995*1.993

Discuss

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25

Trial and error or Newtons method

When 0.10 moles CO and 0.20 moles of H2 are placed in a 1-L vessel at temperature T and allowed to come to equilibrium. CO (g) + 3 H2 (g) CH4 (g) + H2O (g) Kc = 9.7 What are the concentrations of various species? Solution (note the strategy please) CO (g) + 3 H2 (g) CH4 (g) + H2O (g) start 0.10 0.20 0 0 change - x - 3x +x +x eqlbm 0.1-x 0.2-3x x x (= ?) x = Kc = 0.05* 400 0.06 15174 0.04 52 0.03 11.3 Kc = (x)2 / (0.1-x) (0.2-3x)3 = 9.7 0.029 8.21 Too difficult to solve.You need not worry. Trial-and-error (Newtons method) results shown>> 0.0299 9.50 *x < 0.1
16 Chemical Why cannot use successive approximation? Equilibrium x=0.44 is unreasonable. The first
26

Apply math skill

Exactly 0.0100, 0.0100 and 0.0200 moles of H2, I2, and HI are mixed in a 1-L vessel, and then raised to 277 K, at which Kc = 50.3. What concentration will increase? Solution (summary) H2 (g) + I2 (g) = start 0.0100 0.0100 change -x -x eqlbm [ ] 0.01-x 0.01-x value 0.0044 0.0044 (0.02+2x)2 = 50.3 (0.01-x)2 Determine from Qc What are the equilibrium concentrations of H2, I2 and HI?

2 HI 0.0200 +2x 0.02+2 x 0.0312 M

assume

x = 0.00560 (0.02+2x) > > note > = 7.09 (0.01-x)

27

16 Chemical Equilibrium

Successive approximation
For 2 H2S (g) = 2 H2 (g) + S2 (g) Kc = 4.2e-6 at 831oC What is [S2] when 0.0700 mol H2S is allowed to reach equilibrium in a 1.00-L vessel.

Solution: 2 H2S (g) = 2 H2 (g) + S2 (g) 0.0700-2x 2x x (2x)2 x = 4.2e-6 x = 3(4.2e-6*0.07002/4) = 1.73e-3 (0.0700-2x)2 assume 0
(2x)2 x = 4.2e-6 x = 3(4.2e-6*0.06652/4) = 1.67e-3 (0.0700-2*0.00173)2 successive inclusion Carry out the calculation plse
4x316 Chemical Equilibrium 3 = 4.2e-6 x = (4.2e-6*0.06672/4) = 1.67e-3 (0.07-2*0.00167)
28

Equilibria involving solvents

Since [solvent] is essentially constant, it does not appear in Kc expression. You just have to know and apply. CH3COOC2H5 (aq) + H2O (l) = CH3COOH (aq) + C2H5OH (aq) [CH3COOH] [C2H5OH] Kc = [CH3COOC2H5] [ H2O]

[CH3COOH] [C2H5OH] Usually, Kc = Kc [ H2O] = [CH3COOC2H5]

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Equilibria involving solvents - application

For the reaction, CH3COOC2H5 (aq) + H2O (l) = CH3COOH (aq) + C2H5OH (aq) Kc = 0.25 at 25oC. Calculate [C2H5OH] at equilibrium starting with 1.00 M of ethyl acetate. Solution: CH3COOC2H5 (aq) + H2O (l) = CH3COOH (aq) + C2H5OH (aq) 1.00 x x x= [C2H5OH ] x2 = 0.25 x2 + 0.25 x 0.25 = 0 (1.00 x)

0.25 + 0.252 4(-0.25) x = = 0.39 M 2

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Equilibrium Calculations a summary

Several methods have been introduced in evaluating x Simple method Approximation Trial and error (Newtons method) Recognize math relationship (taking square root on both sides) Successive approximation

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31

Kp and Kc; Kp = Kc (R T) {c+d-(a+b)}

The equilibrium constants depends on the units used for quantities. In general, the equilibrium constant is represented by K

When concentrations are used, Kc is the notation; when partial pressures are used, Kp is used
Since PV = n R T,

P = (n/V) R T = [ ] R T

[ ] = (n / V) is the concentration

For the reaction a A + b B c C + d D PCc PDd [C]c [D] d (R T)c + d Kp = = = Kc (R T){c+d-(a+b)} PAa PBb [A]a [B] b (R T)a + b

See page 635

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Kp more appropriate for

H2O (l) = H2O (g) Kp = vapor pressure of water

H2O (s) = H2O (g)

Kp = vapor pressure of ice

At the triple point, its obvious that vapor pressure of ice = vapor pressure of water if these are equal, the three phases are present. CaCO3 (s) = CaO + CO2 Kp = partial v. p. of CO2

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33

Kc and Kp conversion
For 2 H2S (g) = 2 H2 (g) + S2 (g) What is Kp? Kc = 4.2e-6 at 831oC

Solution: Kp = Kc (R T){c+d (a+b)} (recall or derive) = Kc (R T)(2+1 2) = 4.2e-6 *8.314 kJ mol 1 K 1 * (831+273) K = 3.9e-2
2 H2S (g) = 2 H2 (g) + S2 (g) 0.0667 3.34e-3 1.67e-3 612 kPa 30.7 15.3 6.04 atm 0.30 0.15 Kp confirmation Kc = 4.2e-6 at 831oC Kp = 3.9e-2 J mol 1 K 1 at 831oC Kp = 3.7e-4 L atm mol 1 K 1
34

16 Chemical Equilibrium

Le Chateliers Principle
The system will restore its equilibrium after changing conditions. An open bottle of water will dry eventually, because the partial pressure never reach equilibrium (removing vapor pressure). Increase pressure will increase the formation of NH3 in N2 (g) + 3 H2 (g) = 2 NH3 (g) Hof = 91.8 kJ Increase T will decrease the formation of NH3 in this exothermic reaction. How does [CH4] change when pressure increase for an equilibrium of CO (g) + 3 H2 (g) CH4 (g) + H2O (g)? Increasing pressure tends to reduce the number of molecules. Study sections: 16.6
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35

Le Chateliers Principle cont.

Possible changes: Temperature, T Increase T favors forward reaction in an endothermic reaction but favors reverse reaction in an exothermic reaction Pressure, P and volume V Pressure and volume are related. Decreases of volume increase the pressure Amounts of product and reactants Increase amounts of reactants, products or both increases P and V

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36

Henri Louis Le Chatelier

(1850-1936) A mining engineer investigated structure of metals and alloys, translated work of Gibbs into French stated Henricus Vant Hoffs (Nobel Prize 1901) theory in word and wrote on industrial efficiency and labor management relations Scientist would be wise to refrain from using the mathematical equation unless he understands the theory that it represents, and can make a statement about the theory that does not consist just in reading the equation. L. Pauling
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Effect of a catalyst
There are two factors regarding the speed of reactions: kinetics and thermodynamics. Kc and Kp are thermodynamic parameters, related to G o. Thus, the equilibrium constants are not affected by a catalyst. Catalyst only affect reaction constant k, which is related to the activation energy. Reaction See page 643-646
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kinetic

thermodynamic

Equilibria

- Summary

Apply stoichiometry to equilibrium mixture in a system Write reaction quotient and equilibrium constant expression. Rewrite Qs and Ks when the equations change. Predict direction of reaction by comparing Q and K. Evaluate Ks from some know conditions.

Know how energies H and G are related to equilibrium constants.

Use various methods to evaluate concentrations of an equilibrium system. Apply Le Chateliers principle to predict changes in P, [ ], and T.

Separate kinetic and thermodynamic factors of reactions.

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39

Equilibrium review -1
Recall that and G = Go + R T ln K = 0 Go = R T ln K, or ln K = Go / R T

Since Go refers to the standard condition (1 atm and 273K), units for pressures to calculate Kp should theoretically be in atm. However, the standard condition is redefined from time to time, and one has to be aware of the relationship here for engineering calculations. In Chem123, we take a simple approach to specify the units and adhere to the unit atm for pressures.

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40

Equilibrium review 2
Compare with slide 23 At 600K, the partial pressure of NO2 in a equilibrium mixture is 0.10 atm, N2O4 = 2 NO2 Kp = 3.06 L atm mol 1 K 1 What is the partial pressure of N2O4? What is the percent of dissociation of N2O4? What percentage of molecules are NO2?

Solution:
N2O4 = 2 NO2 Kp = 3.06 L atm mol 1 K 1 x 0.10 let x be the unknown 0.102 / x = 3.06; x = 0.12/3.06 = 0.0033 atm P(N2O4) percent dissociated = 0.05 / (0.0033+0.05) = 0.94 = 94% % of NO2 molecule = 0.10/(0.10+0.0033) = 0.97 = 97%
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At 1123K, Kc = 0.153 for the reaction: C(s) + CO2 (g) = 2 CO (g) Ho = 172.5 kJ What is Kp? If initially the partial pressure of CO2 was 1.50 atm, what is the total pressure at equilibrium? How will the equilibrium shift if temperature is decreased to 900K? Solution:

Equilibrium review - 3

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42

At 1123K, Kc = 0.153 for the reaction: C(s) + CO2 (g) = 2 CO (g) Ho = 172.5 kJ What is Kp? If initially the partial pressure of CO2 was 1.50 atm, what is the total pressure at equilibrium? How will the equilibrium shift if temperature is decreased to 900K? Solution: R in L-atm mol-1 K-1 Kp = 0.153 (R T)1 = 0.153(0.08206*1123) = 14.1 C(s) + CO2 (g) = 2 CO (g) 1.50-x 2x equilibrium pressure (2x)2 / (1.50 x) = 14.1; 4x2 + 14.1x 21.2 = 0
x = {- 14.1 + (14.12 + 4*4*21.1)} / (2*4) = 1.13 atm total pressure = 1.50-x+2x = 1.50+x = 1.50 + 1.13 = 2.63 atm P(CO2) = 1.50 1.13 = 0.37 atm; P(CO) = 2*1.13 = 2.26

Equilibrium review - 3

P(CO) decreases at 900K (<1123K) in the endothermic reaction (+ Ho). shift left 43
16 Chemical Equilibrium