CHEM 254

EXP 10
Chemical Equilibrium - Homogeneous and Heterogeneous
Equilibrium

A reaction at constant temperature and pressure can be expressed in terms of the reaction Gibbs
energy. The reaction Gibbs energy is defined as the slope of the graph of the Gibbs energy plotted
against extent of reaction (Figure 1).

If rG<0 the forward reaction is spontaneous

If rG>0 the reverse reaction is spontaneous
Gibbs energy, G

If rG=0 the reaction is at equilibrium

rG=0 rG>0
rG<0

extent of reaction,

Figure 1. Variation of reaction Gibbs energy as a function of extent of reaction

For a reaction with stoichiometric coefficients J, the amount of reactants and products change by

and the change in Gibbs energy is

where is the chemical potential of species J.

The chemical potential of species is related to its activity

used

where

At equilibrium thus

For a general equation;

aA + bB = cC + dD

where ’s are activities, ’s are activity coefficients and C0 is the standard concentration, (1M)

At infinite dilution activity coefficients are equal to one. Thus, for dilute solutions equilibrium constant
may be calculated using concentrations instead of activities.

When all the reactants and products are in the same phase then the equilibrium established is named
as homogenous equilibrium. If more than one phase is present in the equilibrium mixture then a
heterogeneous equilibrium is achieved.

Purpose: The aim of this experiment is to study the homogeneous equilibrium process of an
esterification reaction in the presence of HCl as catalyst.

CH3COOH +C2H5OH CH3COOC2H5 + H2O

and heterogeneous equilibrium of distribution of I2 in two phases

I2 (CHCl3) I2 (H2O)

Apparatus and Chemicals

Part I. Homogenous equilibrium

Apparatus: Nine 100 mL, glass stoppers, narrow-mouth bottles, pipettes, burettes, flasks.
Chemicals: Glacial acetic acid, ethanol, ethyl acetate, 3M HCI, 1.0 M NaOH, phenolphthalein.

Part II. Heterogeneous equilibrium

Apparatus: Six 250 mL glass-stoppers, pipettes, burette, flasks, temperature (25°C).

Chemicals: 0.01 M and 0.1 M KI, saturated Iodine Solution, 0.1 M and 0.02 M standard sodium
thiosulfate

Part I. Homogeneous Equilibrium

In the esterification reaction, as stoichiometric coefficients are all equal to one, equilibrium constant
can be also expressed in terms of number of moles of reactants and products;

CH3COOH +C2H5OH CH3COOC2H5 + H2O

[Ester] . [water] n(ester) . n(water)

K= =
[acid] . [ethanol] n(acid) . n(ethanol)

The enthalpy of the reaction is very close to zero. Thus, it can be assumed that the equilibrium
constant is almost independent of temperature. In general, HCl is used as a catalyst to increase the
rate of the reaction.

Procedure

Caution: The mixtures used in Part A-Homogenous Equilibrium should be prepared in bottles as
described in Table 1, one week before the assigned experiment day and left at room temperature for
one week. The bottles should be shaken from time to time during this period.

On the assigned experiment day, first prepare the solutions for Part II-Heterogeneous Equilibrium.
Then, while waiting for the establishment of the equilibrium for Part II, continue the experiment on
Homogenous Equilibrium starting from Part I.2.

1. Prepare the following mixtures in 9 different bottles and close the bottles and leave solutions for one
week for establishment of equilibrium.
 Table 1. Volume of each chemical that should be mixed to prepare the solutions

Bottle
3 M HCl, mL Ethanol, mL Acetic acid, mL Ester, mL Water, mL
number

1 5 - - 5 -

2 5 - - 3 2

3 5 - - 2 3

4 5 4 1 - -

5 5 3 2 - -

6 5 2 3 - -

7 5 1 4 - -

8 5 - 1 4 -

9 5 1 - 4 -

2. Record density of each reactant and product on your report sheet.

3. Transfer 5 mL of each solution into nine different erlenmeyers.

4. Add 1 drop of phenolphthalein to each solution.

5. Titrate with 1.0 M NaOH. Record the volume of NaOH consumed up to the end point (Report Sheet-
Table 1)

Treatment of Data

1. Calculate the initial number of moles of acetic acid, HAc, ethanol, Et, and ester, Es. (Report Sheet,
Table 1)

ni,0 = mi / MWti = di x Vi / Mwti

2. Calculate the initial number of moles of water taking into account the amount of H 2O introduced by
adding HCl (Report Sheet, Table 1). Assume dsolution= d water =1.0 g/mL

mHCl = nHCl x MWtHCl =MHCl x VHCl x MWtHCl

msol = mass of solution = 1.0 g/mL x V

mwater = mass H2O added + mass of H2O due to HCl addition = madd + (msol - mHCl)

nwater,0 = mwater / Mwt

3. For Solutions 1-3

CH3COOH + C2H5OH CH3COOC2H5 + H2O

initial [Ester]0 [water]0

at equilibrium x x [Ester]0 - x [water]0 - x

x = (nHac)eq = nethanol

(nHAc)eq = MNaOH x Vtitration

(nEs)eq = (nEs)0 - x

(nwater)eq = (nwater)0 - x

4. For Solutions 4-7

CH3COOH + C2H5OH CH3COOC2H5 + H2O

initial [HAc]0 [ethanol]0 [water]0

at equilibrium [HAc]0 - x [ethanol]0 - x x [water]0 + x

(nHac)eq = MNaOH x Vtitration

x = (nHAc )0 - (nHAc )eq

(nEt) eq = (nEt)0 -x

(nEs )eq= x
(nwater )eq= (nwater)0 + x

5. Calculate the equilibrium moles of reactants and products in solutions 8-9.

6. Calculate K for each solution, and the average value. Determine the standard deviation. Discuss
possible sources of errors.

Part II. Heterogeneous Equilibrium

The reaction between I2 and I- is an homogenous equilibrium in aqueous solution.

- -
I2 + I I3

As the amount of I2 that dissolves in water is very small, the equilibrium concentrations are very small
and thus can be used instead of activities.

When CHCl3 is added to the above equilibrium solution, molecular iodine I2 is distributed in water and
CHCl3 phases according to the following heterogeneous equilibrium process. The two immiscible
phases, water (polar) and CHCl3 (nonpolar) are separated as shown in Figure 2.
 I2 (water) I2 (CHCl3)

Figure 2. Separation of phases

Procedure

1. Prepare the following solutions

Solution 1: 35 mL I2 saturated CHCl3 (CHCl3 phase) + 100 mL H2O (aqueous phase)

Solution 2: 35 mL I2 saturated CHCl3 (CHCl3 phase) + 75 mL 0.01 M KI (aqueous phase)

Solution 3: 35 mL I2 saturated CHCl3 (CHCl3 phase) + 35 mL 0.1 M KI (aqueous phase)

2. Place the solutions into water bath at 25°C and wait for 40 min. Shake the solutions at every 5 min.
Then wait for 10 min for the separation of two phases. While waiting for establishment of
equilibrium, continue on the experiment Homogenous Equilibrium, Part I - 2.

3. From each solution withdraw volumes of samples from each aqueous and CHCl3 phases as given in
the following Table into six different erlenmeyer flasks. Caution: While withdrawing sample from
the CHCl3 layer, be careful not removing sample from the aqueous layer Blow very slowly air
through the pipette to minimize contamination.

Table
Solution 1 Solution 2 Solution 3
Vaq/KI withdrawn, mL 50 50 25
V CHCl3 withdrawn, mL 25 25 25
4. To each aqueous phase:

i. Add 10 mL 0.10 M KI (KI is added in excess amount to convert almost all I2 to I3- in the aqueous
phase to avoid loss of I2 during the experiment by evaporation.)

ii. Titrate with 0.02 M S2O32- until the color turns to very light Brown (color of light tea).

- 2- - -
I3 + 2 S2O3 3I + S4O6

iii. Add 2 mL starch and continue titration with S2O32- until the solution becomes colorless. Record the
2-
volume of S2O3 (Report Sheet Table 3).

5. To each CHCl3 phase:

i. Add 10 mL 0.10 M KI.

ii. Titrate with 0.10 M S2O32- - until the color turns to color of light tea.

iii. Add 2 mL starch as indicator and continue titration with S2O32- until the solution becomes colorless.
Record the volume of S2O32- (Report Sheet Table 3).

Treatment of Data

1. Calculate KD from the amount of I2 distributed in each phase in solution 1

For both aqueous and CHCl3 phases

n(I2) = n( I3- ) = 1/2 x n(S2O32-) = MS2O3 x VS2O3

[ I2 ] = n(I2) / V

where V is the volume of the aqueous or CHCl3 phase used in the titration

Calculate KD =

2. Calculate the equilibrium concentrations of I-, I2 and I3- in solutions 2 and 3

For both solutions, when the equilibrium is established in the aqueous phase

- -
I2 + I I3

-
[I2]aq,eq [I ]0-x x

[ I2 ]aq,eq in the aqueous phase can be calculated using the heterogenous equilibrium process

[ I2 ] aq,eq = KD x [ I2 ]CHCl3

2-
[ I2 ] CHCl3 = n(I2) / V =1/2 x n(S2O3 ) / V CHCl3 = MS2O3 x VS2O3/ V CHCl3
 - -
The amount I3 in aqueous phase is the sum of the amount of I 3 produced by the equilibrium process
- -
n([I3 ])water, eq and the amount of I3 produced by the conversion of I2 upon addition of KI before the
-
titration by n(I3 )due to reaction of iodine with KI added.

n( I3- ) aq, total = 1/2 x n(S2O32-) = MS2O3 x VS2O3

[ I3- ] aq, total = n( I3- ) aq, total / Vaq = [ I3- ]aq, eq + [ I3- ]

[ I3-] = [ I2 ] aq,eq

- -
[ I3 ] aq , eq = [ I3 ] aq, total - [ I2 ] aq =x=

- -
[ I ]eq = [ I ]0 - x

- -
Calculate K for the reaction I2 + I I3

Questions

1. State Le Chateliers’s Principle.

2. State the factors that alter the composition of an equilibrium mixture based on Le Chateliers’s
Principle.
3. Explain the effect of the changes on reactant or product when a stress is applied to a system.
4. Determine the reaction direction when a system at equilibrium reacts to a stress applied to the
system including changes in concentrations, pressure and volume, or temperature.
5. Describe the effect of adding a catalyst to a system at equilibrium. In our system, how does
the strong acid function as the catalyst?
6. Explain the factors that affect the equilibrium constant.
 DATA SHEET Experiment 11 - Homogeneous and
Heterogeneous Equilibria

Group Number: Date:

Assistant name and signature:

Part I. Homogeneous Equilibria

1. Initial concentrations

nHAc =

nEt =

nEs =

2. mH2O = madd + (msol - mHCl) =

nH2O =

Table 1. Initial number of moles of reactants and products and VNaOH consumed

Solution nHac nEt nEs Water(mL) VNaOH(mL)

3. For Solutions 1-3

CH3COOH + C2H5OH CH3COOC2H5 + H2O

[Ester]0 [water]0 initial

x x [Ester]0 - x [water]0 - x at equilibrium

 x = (nHAc)eq = (nEtl)eq

(nHAc)eq =

(nEs)eq =

(nwater)eq =

4. For Solutions 4-7

CH3COOH + C2H5OH CH3COOC2H5 + H2O

[HAc]0 [ethanol]0 [water]0 initial

[HAc]0 - x [ethanol]0 - x x [water]0 + x at equilibrium

(nHAc)eq =

x=

(nEt)eq =

(nEs)eq =

(nwater)eq =

5. For Solutions 8-9

6. K for each solution

Table 2. The number of moles of reactants and products

 Solıtion n(HAc)eq n(Et)eq n(Es)eq n(H2O) eq K

K (average) =
Standard deviation =

Part II. Heterogeneous Equilibria

Table 3.
VS2O3(mL)
aqueous phase
Solution 1
CHCl3 phase
aqueous phase
Solution 2
CHCl3 phase
aqueous phase
Solution 3
CHCl3 phase

1. n( I2 )aq =

[ I2 ] CHCl3 =

n( I2 ) CHCl3 =

[ I2 ] aq =

KD =

2. For solution 2

[ I2 ] CHCl3 = n(I2) / V =1/2 x n(S2O32-) / V(CHCl3) = M(S2O32-) x V(S2O32-)/ V(CHCl3) =

 [ I2 ] aq,eq = KD x [ I2 ] CHCl3 =

n( I3- ) aq, total = 1/2 x n(S2O32-) = M(S2O32-) x V(S2O32-) =

[ I3- ] aq, total = n( I3- ) aq, total / Vaq = [ I3- ]aq, eq + [ I3- ]due to reaction of iodine with KI added

[ I3-]due to reaction of iodine with KI added = [ I2 ] aq,eq

[ I3- ] aq , eq = [ I3- ] aq, total - [ I2 ] aq = x=

- -
[ I ]eq = [ I ]0 - x

3. For solution 3

[ I2 ] CHCl3 =

[ I2 ] aq,eq =

n( I3- ) aq, total =

[ I3- ] aq, total =

[ I3-]due to reaction of iodine with KI added =

[ I3- ] aq , eq =

[ I- ]eq =

4. Calculate the equilibrium constant K

[ I2 ] aq,eq = [ I2 ] CHCl3 [ I3- ] aq, total [ I- ]eq K

Solution 1
Solution 2

5. Compare K values obtained for solutions 2 and 3. What are the possible reasons for the difference
in these two values.