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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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.

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

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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

When potential energies are the same. Water flows from a high potential-energy place to a low potential-energy place. Molecules still exchange kinetic energies during collision.Chemical Equilibrium – a dynamic process Chemical equilibrium is a state of a system when reaction rates in both directions are equal. Equilibrium is a dynamic rather than static process. water stops flowing. Changes continue at the molecular level. Heat is energy flowing from a high temperature object to a low temperature object. Watermolecule diffusion continues. Equilibrium is reached when the temperatures are the same. 16 Chemical Equilibrium 5 . but the macroscopic properties stay the same.

often also on temperature. solubility. distribution of a substance in two immiscible liquids are typical equilibria. It is a function of temperature. Vapor pressure of a liquid is the pressure of the vapor in equilibrium with a liquid. Distribution (or equilibrium) coefficients of a substance in immiscible liquids are useful guides for the separation of mixtures into components. depends on the substance and the solvent.Some Typical Equilibria Macroscopic properties such as vapor pressure. amount in solution in equilibrium with solid. 16 Chemical Equilibrium 6 . Solubility.

The reaction quotients For any chemical reaction in a system. [C]c [D]d Q = —————— [A]a [B]b for example. Text: 16-5 defines Q & 16-1 defines K. [NO2]2 Q = —————— [N2O4] Know the definition of Q. (Q is reaction quotient) for N2O4  2 NO2 16 Chemical Equilibrium 7 . aA+ b B c C + d D we can always write a quotient.

what are the units for Q? 16 Chemical Equilibrium 8 . 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.Expressions for reaction quotients For the ionization of an acid.

See 16-3 Q=Q2 Note the relationships 16 Chemical Equilibrium 9 .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.

the reaction goes forward if Q = K. the system is at equilibrium if Q > K.Equilibrium constant .mass action law When a chemical reaction in a closed system is at equilibrium. M(a+b-c-d) if M is used. K. For a chemical reaction in a closed system. the reaction goes backward See 16-5 & 16-3 | to increase [product] |the law of mass action | to decrease [product] 10 16 Chemical Equilibrium . the reaction quotient is defined as the equilibrium constant. If Q < K. which depends on T. 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.

03 (0.11 0.11.03) K = —————— = 9. 0.07) (0.Evaluating K The equilibrium mixture is found to contain 0.03) (0. CH4 and H2O respectively for the reaction: CO (g) + 3 H2 (g)  CH4 (g) + H2O (g) What is the equilibrium constant. H2.03 and 0.11)3 What governs the quantitative relationship 16 Chemical Equilibrium among equilibrium mixtures? 11 .03 moles of CO.07.07 0. K? Solution CO (g) + 3 H2 (g)  CH4 (g) + H2O (g) start 0. 0.03 0.7 (0.

03 [] 0.03) / (0.Evaluate quantities When 0.7 16 Chemical Equilibrium 12 .03 moles H2O for the reaction: CO (g) + 3 H2 (g)  CH4 (g) + H2O (g) What is the equilibrium constant.10 moles CO and 0.1-x 0.03 0. The mixture is found to contain 0.20 0 0 change .11 0.10 0.03) eqlbm 0.20 moles of H2 are placed in a 1-L vessel at temperature T and allowed to come to equilibrium.07) (0.03 0.03 K = (0. K? Solution (note the strategy please) CO (g) + 3 H2 (g)  CH4 (g) + H2O (g) start 0.x .3x +x +x (x=0.07 0.03) (0.2-3x 0.11)3 = 9.

01 K = (0.01 0.08 moles CO.09) (0.08+0.09 0.11 0.08 0 change .01) / (0.03 0.01 [] 0. The mixture is found to contain 0.07) (0. and 0.11)3 = 9.14-0. K? Solution (note the strategy please) CO (g) + 3 H2 (g)  CH4 (g) + H2O (g) start 0.08-0.08+x +x (x=0. 0.01) eqlbm 0.x .08 moles of CH4 are placed in a 1-L vessel at temperature T and allowed to come to equilibrium.01 0.08 0.Evaluate quantities When 0.01 moles H2O for the reaction: CO (g) + 3 H2 (g)  CH4 (g) + H2O (g) What is the equilibrium constant.07 0.3x 0.14 0.7 16 Chemical Equilibrium 13 .14 moles of H2.

Entropy We all know that heat flow from a high-T object into a low-T object. What causes change when no apparent energy is involved? 16 Chemical Equilibrium 14 . E. divided by T. This type of change can be described as due to increase of entropy. Entropy is also associated with randomness of ordering. Entropy S is the amount of energy transferred. E S = ———— or TS = E T Entropy increases for spontaneous changes (reactions).

Heat of fusion of ice (molar mass 18) is 6 kJ/mol.0 g of ice at 273 K.0 kJ too little to change the temperature of the entire system appreciably from 300 K. Solution: Since the amount of heat for melting the ice is 6 *(3/ 18) = 1.33 J/K (entropy unit) What is the molar entropy for ice melting? +6000 J mol–1 / 273 K = 22 J mol –1 K –1 (entropy unit mol–1) 16 Chemical Equilibrium 15 . What is the change in entropy when the system is at equilibrium. Thus the entropy change is – 1/300 + 1/273 = 3.Entropy calculation A system consists 10.0 L of water at 300 K and 3.3e – 4 kJ/K = 0.

Gibbs (1839-1903) New Haven.S.A. USA First Doctorate (1863 Yale) in Engineering of U. 1871 Professor of mathematics and physics at Yale Unassuming in manner. he went far toward realizing the ideal of the unselfish. never showing impatience or irritation. .Bumstead lunar crater Gibbs 16 Chemical Equilibrium 16 . the greatness of his intellectual achievements will never overshadow the beauty and dignity of his life. genial and kindly in his intercourse with his fellowmen. influenced by Kirchhoff & Helmholtz. devoid of personal ambition of the baser sort or of the slightest desire to exalt himself. Studied in Europe. Christian gentleman.Josiah W. In the minds of those who knew him. Connecticut.

Gibbs free energy. What drives physical and chemical changes? 16 Chemical Equilibrium 17 . Similar to Ho. Gibbs defined a function together with enthalpy of change. for differences of these quantities Since H is negative and S is positive for spontaneous change. Gibbs free energy is the maximum amount of available energy in any change. H. Go is the Gibbs free energy at the standard T and P. G or G Following the definition of entropy S. and it unified enthalpy and entropy for changes. Gibbs free energy is negative for all spontaneous changes. G=H–TS or G = H – T S now called Gibbs free energy.

Go = – R T ln K.Energy and equilibrium constant K A quantity called Gibbs free energy. G = Go + R T ln K = 0 Thus. G is negative for spontaneous reaction G is positive for non-spontaneous reaction The G is related to the reaction quotient Q. is defined as the maximum amount of energy from a chemical reaction for doing work. G = Go + R T ln Q When a system is at equilibrium there is no available energy. G. 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 16 Chemical Equilibrium 19 .

decomposes. When 4. 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.An Example Hydrogen iodide.442 mol I2. 16 Chemical Equilibrium 20 .00-L vessel at 458oC. 2 HI  H2 + I2 The amount of I2 can be determined from the intensity of the violet color of I2. the equilibrium mixture was found to contain 0.00 mol of HI was placed in a 5. HI.

00 L = 0.00 mol of HI was placed in a 5.0 mol / 5.0884 M Know your strategy  16 Chemical Equilibrium 21 .442 mol I2. 2 HI  H2 + I2 The amount of I2 can be determined from the intensity of the violet color of I2. HI.Analysis of Example Hydrogen iodide. What is the value for K for the decomposition of HI at this temperature? Analysis of the problem: [HI]0 = 4. decomposes.800 M [I2]equilibrium = 0.442 mol / 5.00-L vessel at 458oC. When 4. the equilibrium mixture was found to contain 0.0 L = 0.

0884 M 0.6232)2 Skill: re-interpret question.Calculate Kc Example 14. Evaluate other quantities and K from known start conditions and experimental results Evaluate Go 16 Chemical Equilibrium 22 .0884 M from experiment x 0. start change equlbm value 2 HI (g) = H2 (g) + 0.0884 Kc = ——————— = 0.3 The equilibrium concentration of various species are given below their symbols.800-2x x 0.0884*0.6232 0.0884 I2 (g) 0 = 0.800 0 =? =? 0.0201 (0.

an equilibrium mixture contains 70% NO2 by mass in a tube of NO2 and N2O4. 0. 0. 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 NO2.326 mol N2O4) find volume from pressure for all (45.00717 M) evaluate Kc (equation dependent) 16 Chemical Equilibrium 23 .Evaluate Kc Compare with slide 41 At 300 K and 1 atm.49 L) find concentration from volume (0. Evaluate Kc for the reaction.0335 M NO2.

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.0157 8.20e-3 at 300 K.Application of Kc For N2O4 (g) = 2 NO2 (g) Kc = 4. 4x2 + 0.0042 x – 0.0200-x N2O4 (g) = 2 NO2 (g) 0.54e-3 M 24 .0200-x 2x (2x)2 ———— = 4e-3 (K) 0.265e-5)} x = ———————————————————— = 4.0000926 = 0 -0.100 mol of N2O4 is placed in a 5.00463 + {(4.27e-3 2*4 16 Chemical Equilibrium N2O4 (g) = 2 NO2 (g) 0. What are the equilibrium concentrations if 0.63e-3)2 – 4*4*(-9.

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 1.3x +2x (= ?) eqlbm 1.0*2.03/4 = 2e-5 x = 4.0-x)(2.995*1.995 M [H2] = 1.0-3x 2x (2 x)2 —————— = 1e-5 (1-x)(2.0-3x)3 x2 = 1e-5*1.0 2.993 Discuss 16 Chemical Equilibrium 25 .99 [NH3] = 9e-3 Checking (2*4.0-3x)3 4x2 —————— = 1e-5 (1.5e-3 (justified) Approximations Results: [N2] = 0.x .0 0 change .5e-3)2 ————— = 1e-5 0.0-x 2.

7 What are the concentrations of various species? Solution (note the strategy please) CO (g) + 3 H2 (g)  CH4 (g) + H2O (g) start 0.x .2-3x)3 = 9.50 *x < 0.1-x 0.3x +x +x eqlbm 0.10 0.Trial and error or Newtons method When 0.21 Too difficult to solve.06 15174 0.0299 9.2-3x x x (= ?) x = Kc = 0.20 moles of H2 are placed in a 1-L vessel at temperature T and allowed to come to equilibrium.You need not worry.3 Kc = (x)2 / (0.1-x) (0.20 0 0 change .029 8.03 11.7 0.10 moles CO and 0. The first 26 . Trial-and-error (Newton’s method) results shown>> 0. CO (g) + 3 H2 (g)  CH4 (g) + H2O (g) Kc = 9.05* 400 0.44 is unreasonable.1 16 Chemical Why cannot use successive approximation? Equilibrium x=0.04 52 0.

I2 and HI? 2 HI 0.02+2 x 0.01-x)2 Determine from Qc What are the equilibrium concentrations of H2.Apply math skill Exactly 0. 0. and HI are mixed in a 1-L vessel.3. and then raised to 277 K.02+2x)2 ————— = 50.0100 0. What concentration will increase? Solution (summary) H2 (g) + I2 (g) = start 0.0100 and 0. I2.09 (0.0100.0312 M assume x = 0.01-x 0.01-x) 27 16 Chemical Equilibrium .0200 moles of H2.02+2x) > > note > ————— = 7.00560 (0.0200 +2x 0.0044 (0.3 (0.0100 change -x -x eqlbm [ ] 0.01-x value 0. at which Kc = 50.0044 0.

0700-2*0.73e-3 (0.2e-6 x = 3(4.2e-6 x = (4.0700 mol H2S is allowed to reach equilibrium in a 1.2e-6*0.0700-2x)2 assume 0 (2x)2 x ————— = 4. Solution: 2 H2S (g) = 2 H2 (g) + S2 (g) 0.07-2*0.67e-3 (0.0700-2x 2x x (2x)2 x ————— = 4.07002/4) = 1.00-L vessel.06672/4) = 1.2e-6 x = 3(4.00173)2 successive inclusion Carry out the calculation plse 4x316 Chemical Equilibrium 3 = 4.2e-6*0.00167) 28 .Successive approximation For 2 H2S (g) = 2 H2 (g) + S2 (g) Kc = 4.06652/4) = 1.67e-3 (0.2e-6*0.2e-6 at 831oC What is [S2] when 0.

Kc = K’c [ H2O] = ———————————— [CH3COOC2H5] 16 Chemical Equilibrium 29 .Equilibria involving solvents Since [solvent] is essentially constant. CH3COOC2H5 (aq) + H2O (l) = CH3COOH (aq) + C2H5OH (aq) [CH3COOH] [C2H5OH] K’c = ———————————— [CH3COOC2H5] [ H2O] [CH3COOH] [C2H5OH] Usually. it does not appear in Kc expression. You just have to know and apply.

Calculate [C2H5OH] at equilibrium starting with 1.00 – x) – 0.252 – 4(-0.Equilibria involving solvents .00 – x x x= [C2H5OH ] x2 ———— = 0. CH3COOC2H5 (aq) + H2O (l) = CH3COOH (aq) + C2H5OH (aq) Kc = 0.25 x2 + 0.25 + 0.application For the reaction.00 M of ethyl acetate.25 x – 0. Solution: CH3COOC2H5 (aq) + H2O (l) = CH3COOH (aq) + C2H5OH (aq) 1.25) x = ———————————— = 0.39 M 2 16 Chemical Equilibrium 30 .25 at 25oC.25 = 0 (1.

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 16 Chemical Equilibrium 31 .

the equilibrium constant is represented by K When concentrations are used. 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 16 Chemical Equilibrium 32 . when partial pressures are used. Kc is the notation. Kp is used Since PV = n R T. Kp = Kc (R T) {c+d-(a+b)} The equilibrium constants depends on the units used for quantities. In general.Kp and Kc.

of CO2 16 Chemical Equilibrium 33 .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. it’s obvious that vapor pressure of ice = vapor pressure of water if these are equal. CaCO3 (s) = CaO + CO2 Kp = partial v. p. the three phases are present.

314 kJ mol – 1 K – 1 * (831+273) K = 3.9e-2 2 H2S (g) = 2 H2 (g) + S2 (g) 0.2e-6 at 831oC Solution: Kp = Kc (R T){c+d – (a+b)} (recall or derive) = Kc (R T)(2+1 – 2) = 4.7 15.3 6.Kc and Kp conversion For 2 H2S (g) = 2 H2 (g) + S2 (g) What is Kp? Kc = 4.15 Kp confirmation Kc = 4.9e-2 J mol 1 K 1 at 831oC Kp = 3.0667 3.04 atm 0.34e-3 1.30 0.2e-6 *8.67e-3 612 kPa 30.2e-6 at 831oC Kp = 3.7e-4 L atm mol 1 K 1 34 16 Chemical Equilibrium .

Le Chatelier’s Principle The system will restore its equilibrium after changing conditions. Study sections: 16. Increase pressure will increase the formation of NH3 in N2 (g) + 3 H2 (g) = 2 NH3 (g) Hof =  91. because the partial pressure never reach equilibrium (removing vapor pressure). 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.8 kJ Increase T will decrease the formation of NH3 in this exothermic reaction.6 16 Chemical Equilibrium 35 . An open bottle of water will dry eventually.

products or both increases P and V 16 Chemical Equilibrium 36 .Le Chatelier’s Principle – cont. T Increase T favors forward reaction in an endothermic reaction but favors reverse reaction in an exothermic reaction Pressure. Decreases of volume increase the pressure Amounts of product and reactants Increase amounts of reactants. Possible changes: Temperature. P and volume V Pressure and volume are related.

Henri Louis Le Chatelier (1850-1936) A mining engineer investigated structure of metals and alloys. translated work of Gibbs into French stated Henricus Van’t Hoff’s (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. Pauling 16 Chemical Equilibrium 37 . L. and can make a statement about the theory that does not consist just in reading the equation.

Kc and Kp are thermodynamic parameters. Thus. Catalyst only affect reaction constant k. which is related to the activation energy.Effect of a catalyst There are two factors regarding the speed of reactions: kinetics and thermodynamics. related to G o. the equilibrium constants are not affected by a catalyst. Reaction See page 643-646 16 Chemical Equilibrium 38 E kinetic thermodynamic .

Rewrite Qs and Ks when the equations change.Summary Apply stoichiometry to equilibrium mixture in a system Write reaction quotient and equilibrium constant expression. Separate kinetic and thermodynamic factors of reactions. Evaluate Ks from some know conditions. Use various methods to evaluate concentrations of an equilibrium system. 16 Chemical Equilibrium 39 . and T. Know how energies H and G are related to equilibrium constants. Apply Le Chatelier’s principle to predict changes in P. [ ]. Predict direction of reaction by comparing Q and K.Equilibria .

and one has to be aware of the relationship here for engineering calculations. However. the standard condition is redefined from time to time.Equilibrium review -1 Recall that and G = Go + R T ln K = 0 Go = – R T ln K. 16 Chemical Equilibrium 40 . we take a simple approach to specify the units and adhere to the unit atm for pressures. units for pressures to calculate Kp should theoretically be in atm. In Chem123. or ln K = – Go / R T Since Go refers to the standard condition (1 atm and 273K).

12/3.06 L atm mol 1 K 1 x 0.10+0. the partial pressure of NO2 in a equilibrium mixture is 0.06. N2O4 = 2 NO2 Kp = 3.Equilibrium review – 2 Compare with slide 23 At 600K.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 = 3.0033) = 0.05) = 0.102 / x = 3.0033+0.10 let x be the unknown 0.97 = 97% 16 Chemical Equilibrium 41 .10 atm.0033 atm P(N2O4) percent dissociated = 0.94 = 94% % of NO2 molecule = 0. x = 0.10/(0.05 / (0.06 = 0.

3 16 Chemical Equilibrium 42 . Kc = 0.50 atm.5 kJ What is Kp? If initially the partial pressure of CO2 was 1. what is the total pressure at equilibrium? How will the equilibrium shift if temperature is decreased to 900K? Solution: Equilibrium review .At 1123K.153 for the reaction: C(s) + CO2 (g) = 2 CO (g) Ho = 172.

1)} / (2*4) = 1.63 atm P(CO2) = 1.50-x+2x = 1.50 – x) = 14.153 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 1.13 = 2.14.1 + (14.153 (R T)1 = 0. 4x2 + 14.1.At 1123K.12 + 4*4*21.153(0.50 – 1.50 + 1.13 atm total pressure = 1.1x –21.3 P(CO) decreases at 900K (<1123K) in the endothermic reaction (+ Ho).2 = 0 x = {.  shift left 43 16 Chemical Equilibrium .37 atm.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 = 0.08206*1123) = 14.26 Equilibrium review . Kc = 0.50+x = 1.13 = 0.1 C(s) + CO2 (g) = 2 CO (g) 1. P(CO) = 2*1.13 = 2.50-x 2x equilibrium pressure (2x)2 / (1.