Chem 157.

1 Experiment 7

Chemical Equilibrium
Alma Lipnica Pabilane Robinson Bryan Cortez Andres

INTRODUCTION
‚You might be chemist if you pronounce unionized as ‘un-ion-ized’, instead of ‘union-ized’.‛

INTRODUCTION
• Thermodynamic functions give conditions for equilibrium • System at constant T and P > EQUILIBRIUM - Gibbs energy is MINIMUM - For a chemical process: depends only on STOICHIOMETRY, not at all on the mechanism of reaction

INTRODUCTION
• Alexander William Williamson (Brit.) > Dynamical equilibrium - when equilibrium is reached in a chemical system, all reaction has NOT ceased, but is still occurring in FORWARD and BACKWARD directions with EQUAL RATE. > Use of double arrows

INTRODUCTION
• Pierre Eugène Marcellin Berthelot and Péan de St. Gilles (1862) > First studied the equilibrium:
CH3COOH(l) + CH3CH2OH(l)  CH3CH2OOCCH3(l) + H2O(l)

> At fixed T, the concentration ratio [CH3CH2OOCCH3][H2O] is always the same [CH3COOH][CH3CH2OH] after equilibrium is reached. Equilibrium constant

INTRODUCTION
• For the reaction at equilibrium: aA + bB  cC + dD > rate forward = rate backward kf[A]a[B]b = kb[C]c[D]d kf = [C]c[D]d = Keq kb [A]a[B]b

INTRODUCTION
• Equilibrium constant can be expressed in: > Pressure (P, for gases): KP > Mole fraction: Kχ > Concentration: KC

OBJECTIVE
• To be able to determine the equilibrium constant (Kc) for the system:
CH3COOH(l) + CH3CH2OH(l)  CH3CH2OOCCH3(l) + H2O(l) acetic acid ethanol ethyl acetate water

EXPERIMENTAL

‚Any delicate and expensive piece of glassware will break before any use can be made of it.‛

EXPERIMENTAL
Flask

(5) 125-mL Erlenmeyer flasks: Flask 1, 2, 3, 4, 5
1 2

V glacial HOAc (mL) 7.0 6.0

V 95% EtOH (mL) 3.0 4.0

3
4

5.0
4.0 3.0

5.0
6.0 7.0

Stopper flasks, mix well; warm over hot plate; let stand 30 mins; (equilibrate)

5

EXPERIMENTAL
pipet. 1 mL from Flask 1 to a 250-mL E-flask; dilute w/ 25 mL dH2O; titrate. standardized 0.5 M NaOH to phenolphthalein endpoint; (3) trials Do the same for Flasks 2, 3, 4, 5. Calculate [HOAc], [EtOH], [EtOAc] and [water] in equilibrium in each flask.

Calculate Kc

‚If an experiment works, something has gone wrong.‛

RESULTS

RESULTS
Table 1. Titration Data, Equilibrium Concentrations, and Calculated Kc for Flask 1
VNaOH (mL) 1 2 27.8 27.9 Equilibrium Concentration [HOAc] 1.388 1.393 1.403 [EtOH] -5.948 -5.943 -5.933 [EtOAc] 10.838 10.833 10.823 [H2O] 11.672 11.667 11.657 -15.32 -15.27 -15.16 Kc

3

28.1

Average Kc ≈ -15.25

RESULTS
Table 2. Titration Data, Equilibrium Concentrations, and Calculated Kc for Flask 2
Trial No. VNaOH (mL) Equilibrium Concentration [HOAc] [EtOH] [EtOAc] [H2O] Kc

1
2 3

20.9
20.8 20.1

1.043 1.038 1.003

-2.916 -2.921 -2.956

9.4362 9.4412 9.4761

10.547 10.552 10.587

-32.71 -32.85 -33.83

Average Kc ≈ -33.13

RESULTS
Table 3. Titration Data, Equilibrium Concentrations, and Calculated Kc for Flask 3
Trial No. 1 2 3 VNaOH (mL) 18.6 18.6 18.0 Equilibrium Concentration [HOAc] 0.929 0.929 0.899 [EtOH] 0.346 0.346 0.316 [EtOAc] 7.8044 7.8044 7.8344 [H2O] 9.1933 223.34 9.1933 223.34 9.2232 254.45 Kc

Average Kc ≈ 233.71

RESULTS
Table 4. Titration Data, Equilibrium Concentrations, and Calculated Kc for Flask 4
Trial No. 1 2 3 VNaOH (mL) 12.8 12.7 0.634 12.9 3.428 6.3523 8.019 23.438 Equilibrium Concentration [HOAc] [EtOH] [EtOAc] [H2O] 0.639 3.433 6.3474 Kc

8.014 23.188

0.644

3.438

6.3424

8.009 22.942

Average Kc ≈ 23.19

RESULTS
Table 5. Titration Data, Equilibrium Concentrations, and Calculated Kc for Flask 5
Trial No. 1 2 VNaOH (mL) 10.2 10.1 Equilibrium Concentration [HOAc] 0.509 0.504 0.499 [EtOH] 6.68 6.675 6.67 [EtOAc] 4.7306 4.7356 4.7405 [H2O] 6.675 9.2834 6.68 9.3992 6.685 9.5175 Kc

3

10.0

Average Kc ≈ 9.40

‚In case of doubt, make it sound convincing.‛

DISCUSSION

DISCUSSION
• Homogeneous Equilibrium > similar phases (solid, liquid, gaseous) • Heterogeneous Equilibrium > different phases of species

DISCUSSION
• Changes in chemical equilibrium > affected by factors such as concentration, temperature and pressure > statement of Le Chatelier
“If a dynamic equilibrium is disturbed by changing the conditions, the position of equilibrium moves to counteract the change.”

DISCUSSION
• Effect of Concentration on Equilibrium > addition or removal of matters in the system: reactants (R) or products (P) > adding R/ removing P - formation of more products; shift to right (forward) > removing R/ adding P - formation of reactant; shift to left (backward)

DISCUSSION
• Effect of Temperature on Equilibrium > addition of heat: Temperature > differs whether exo- or endothermic H2(g) + I2(g)  2HI2(g) + heat (exo) > add’n of heat  shift to left: K > EXOthermic: T, K > ENDOthermic: T, K

DISCUSSION
• Effect of Pressure on Equilibrium > for solids, liquids, aqueous reactants, very little effect; not usually observable > must have at least 1 gaseous matter > reactions involving: > V increase: favored by P > V decrease: favored by P

DISCUSSION
• Equilibrium Constant, K > irreversible reactions: go to completion > after reaction, only products and excess reactants are left in the mixture; products would not react to form reactants > K  ∞; > reversible reactions: products interact to form reactants

DISCUSSION
• at equilibrium, products and reactants coexist > K = ratio of products to reactants - K : more complete reaction - K>1: products dominate the system/ products “favored” - K<1: reactants dominate the system/ reactants “favored” - K=1: neither product nor reactant is favored > K is expressed using coefficients of the balanced equation for the reaction

DISCUSSION
• Calculation of K > K, ratio of activities of Product over Reactant > dissolved substances activities in concentrations: Kc aA + bB cC + dD Kc = [C]c [D]d [A]a [B]b *concentrations are equilibrium concentration

Sample Computations Flask 3 Trial 1
• ninitial,HOAc = (5 mL)(1.049 g/mL) (60.06 g/mol) = 0.087329 mol • Minitial,HOAc = ninitial,HOAc/VT = 0.08733 mol/ 0.01 L = 8.7329 mol/L

Sample Computations Flask 3 Trial 1
• ninitial,EtOH = (5 mL)(0.95)(0.7893 g/mL) (46 g/mol) = 0.081504 mol • Minitial,EtOH = ninitial,EtOH/VT = 0.081504 mol/ 0.01 L = 8.1504 mol/L

Sample Computations Flask 3 Trial 1
• ninitial,H2O = (5 mL)(0.05)(1 g/mL) (18 g/mol) = 0.013889 mol • Minitial,H2O = ninitial,H2O/VT = 0.013889 mol/ 0.01 L = 1.3889 mol/L

Sample Computations Flask 3 Trial 1
• Me, HOAc = (0.499210458 mol NaOH/L)(18.6 mL) 10 mL = 0.9285 mol/L • Mc, HOAc = Mi, HOAc - Mequilibrium, HOAc = 8.7329 – 0.9285 = 7.8044 mol/L

Sample Computations ICE Table for Flask 3 Trial 1
Table 6. ICE Table for Flask 3
[HOAc] I C E 8.7329 -7.8044 0.9285 [EtOH] 8.1504 -7.8044 0.3460 [EtOAc] 0 +7.8044 7.8044 [H2O] 1.3889 +7.8044 9.1933

Sample Computations Kc for Flask 3 Trial 1
Kc = [EtOAc]eq[H2O]eq [HOAc]eq[EtOH]eq Kc = (7.8044)(9.1933) (0.9285)(0.3460) Kc = 2.23 x 102

DISCUSSION
• Gases, activities in Pressures: Kp Kp = Kc(RT)Δng • PURE solids and liquids DO NOT appear in K expression  activity = 1 • Reverse reaction: Kbackward = 1/ Kforward • Reaction multiplied by n: Knew = Kn

Formulas used
• • • • M1V1= M2V2 Moles, n = (Volume)(density)/MW M = n/V Kc = [Products]/[Reactants]

‚No experiment is a complete failure. At least it can serve as a negative example.‛

CONCLUSION

CONCLUSION
• Chemical equilibrium obeys Le Chatelier’s principle • Equilibrium constant is the ratio of activities of products to reactants and can be expressed in concentration, pressure and mole fraction • Only T affect K, not concentration • In expression of K, only the equilibrium concentrations/pressures and coefficients of balanced chemical reaction appear. • Pure solids/liquids not included • Erroneous experimental results

‚Team work is essential, it allows you to blame someone else.‛

RECOMMENDATIONS

RECOMMENDATION
• Accurate measurements of volumes of chemicals > they directly affect the calculations of K • Ensure that the set-up is given enough time to equilibrate • Additional experiment on observing effect of T on K

Q and A

Q&A
1. How is the value of the equilibrium constant affected by the concentration of the reactants used? K is not affected by concentration of reactants used (theoretically).

Q&A
2. How do you explain the observation in #1? Concentrations of reactants do not affect K because they just cause equilibrium to shift to right (reactants added) or left (products added). But, when equilibrium is reached, ratio of [products]/[reactants] remain constant.

Q&A
3. What factors affect the equilibrium constant? As well as most other constants, only temperature affects the equilibrium constant. K’s dependence on T is shown by the relationship lnK = -(ΔG/R) (1/T)

REFERENCES
• Laidler, & Meisser, . (1999). Physical Chemistry. • Factors Affecting Chemical Equilibrium. Retrieved on March 2, 2012 from: http://www.chemistrytutorials.org/content/chemical-equilibrium/factorsaffecting-chemical-equilibrium • Factors Affecting Chemical Equilibrium. Retrieved on March 2, 2012 from http://www.pinkmonkey.com/studyguides/subjects/chem/chap11/c11113 01.asp • Chemical Equilibria Le Chatelier’s Principle: Effect of a Change in Temperature. Retrieved on March 2, 2012 from: http://www.chm.davidson.edu/vce/equilibria/temperature.html • Volland, W. (2005). Equilibrium Equations and Equilibrium Constants. Retrieved on March 2, 2012 from: http://www.800mainstreet.com/7/0007-007-Equi_exp_k.html • Chemical Equilibrium. Retrieved on March 17, 2012 from: http://www.scribd.com/doc/48406157/CHEMICAL-EQUILIBRIUM

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