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 Eugne Marcellin Berthelot and Pan 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: K > 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)

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

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

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) > addn 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)ng 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 Chateliers 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. Ks dependence on T is shown by the relationship lnK = -(G/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 Chateliers 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