PHYSICAL CHEMISTRY LABORATORY I

NUMBER OF THE EXPERIMENT: 10

NAME OF THE EXPERIMENT: CHEMICAL EQUILIBRIUM OF

HOMOGENEOUS AND HETEROGENEOUS EQUILIBRIUM

DATE OF THE EXPERIMENT: 04.04.2018

GROUP NUMBER: 4

NAME OF THE STUDENT: DENİZ KILIÇ

GROUP MEMBERS: ALMİLA NUR GÖZÜTOK

NAME OF THE ASSISTANT: ŞEVKİ CAN CEVHER

Calculations:

Part 1. Homogeneous Equilibrium

1. Initial number of moles of acetic acid, HAc, ethanol, Et, and ester,
Es:
d(Et)= 0.7891 g/mL, d(HAc)= 1.049 g/mL, d(Es)= 0.8971 g/mL
Mwt(Et)= 46.07 g/mol, Mwt(HAc)= 60.05 g/mol, Mwt(Es)= 88.105
g/mol
 Solution 1:
n(Es)= 0.8971 g/mL*5mL/ 88.105 g/mol =0.051 mol
 Solution 2:
n(Es)= 0.8971 g/mL*3mL/ 88.105 g/mol =0.031mol
 Solution 3:
n(Es)= 0.8971 g/mL*2mL/ 88.105 g/mol =0.020mol
 Solution 4:
n(Et)= 0.7891 g/mL*4mL/46.07 g/mol=0.069mol
n(HAc)= 1.049 g/mL*1mL/60.05 g/mol=0.017mol
 Solution 5:
n(Et)= 0.7891 g/mL*3mL/46.07 g/mol=0.051mol
n(HAc)= 1.049 g/mL*2mL/60.05 g/mol=0.035mol
 Solution 6:
n(Et)= 0.7891 g/mL*2mL/46.07 g/mol=0.034mol
n(HAc)= 1.049 g/mL*3mL/60.05 g/mol=0.052mol
 Solution 7:
n(Et)= 0.7891 g/mL*1mL/46.07 g/mol=0.017mol
n(HAc)= 1.049 g/mL*4mL/60.05 g/mol=0.070mol
 Solution 8:
n(HAc)= 1.049 g/mL*1mL/60.05 g/mol=0.017mol
n(Es)= 0.8971 g/mL*4mL/ 88.105 g/mol =0.041mol
 Solution 9:
n(Et)= 0.7891 g/mL*1mL/46.07 g/mol=0.017mol
n(Es)= 0.8971 g/mL*4mL/ 88.105 g/mol =0.041mol
2. mHCl=3mol/L*0.005L*36.46g/mol=0.547g
msol=1.0g/mL*5mL=5g
 Solution 1:
mwater=0+(5-0.547)= 4.453g
nwater4.453g /18.0 g/mol=0.247mol
 Solution 2:
mwater=2+(5-0.547)=6.453g
nwater= 6.453g/18.0 g/mol=0.359mol
 Solution 3:
mwater=3+(5-0.547)=7.453g
nwater= 7.453g/18.0 g/mol=0.414mol
 Solution 4:
mwater=0+(5-0.547)= 4.453g
nwater= 4.453g /18.0 g/mol=0.247mol
 Solution 5:
mwater=0+(5-0.547)= 4.453g
nwater= 4.453g /18.0 g/mol=0.247mol
 Solution 6:
mwater=0+(5-0.547)= 4.453g
nwater= 4.453g /18.0 g/mol=0.247mol
 Solution 7:
mwater=0+(5-0.547)= 4.453g
nwater= 4.453g /18.0 g/mol=0.247mol
 Solution 8:
mwater=0+(5-0.547)= 4.453g
nwater= 4.453g/18.0 g/mol=0.247mol
 Solution 9:
mwater=0+(5-0.547)=4.453g
nwater= 4.453g/18.0 g/mol=0.247mol
3. For solutions 1-3:
CH3COOH + C2H5OH  CH3COOC2H5 + H2O
İ : Es(0) water (0)
E : x x Es(0) – x water (0) – x

İ :initial & E : at equilibrium

x=(nHAc)eq=nethanol
(nHAc)eq = MNaOH x Vtitration
(nEs)eq = (nEs)0 – x
(nWater)eq = (nWater)0 – x
 Solution 1:
x=(nHAc)eq =1mol/L*18.0mL*1L/1000mL=0.018 mol
(nEs)eq = 0.0510mol – 0.018 mol=0.033 mol
(nWater)eq =0.247mol– 0.018 mol=0.229 mol
 Solution 2:
x=(nHAc)eq =1mol/L*16.0 mL*1L/1000mL=0.016 mol
(nEs)eq = 0.031mol – 0.016mol=0.015 mol
(nWater)eq =0.359mol– 0.016 mol=0.343 mol
 Solution 3:
x=(nHAc)eq =1mol/L*12.9mL*1L/1000mL= 12.9*10-3 mol
(nEs)eq = 0.020mol – 0.0129mol=7.10*10-3 mol
(nWater)eq =0.414mol– 0.0129 mol=0.4011 mol
4. For Solutions 4-7

CH3COOH + C2H5OH  CH3COOC2H5 + H2O

İ: M(HAc)0 Et(0) water (0)

E: M(HAc)0 - x Et(0) - x x water (0) + x

n (HAc)eq = M (NaOH) x V (titration)

x = n (HAc)0 - n (HAc)eq
n (Et)eq = n (Et)0 – x
n (Es)eq = x
n (Water)eq = n (Water)0 + x
  Solution 4:
n (HAc)eq = 1mol/L*12.2mL*1L/1000mL=0.0122mol
x =0.017mol – 0.0122mol=4.8*10-3 mol
n (Et)eq = 0.069mol – 4.8*10-3mol=0.0642 mol
n (Es)eq =4.8*10-3 mol
n (Water)eq = 0.247mol+ 4.8*10-3 mol =0.2518 mol
 Solution 5:
n (HAc)eq = 1mol/L*17.6*1L/1000mL=0.0176 mol
x =0.035mol – 0.0176 mol=0.0174 mol
n (Et)eq = 0.051mol – 0.0174 mol=0.0336 mol
n (Es)eq =0.0174 mol
n (Water)eq = 0.247mol+ 0.0174 mol =0.2644 mol
 Solution 6:
n (HAc)eq = 1mol/L*24.8 L*1L/1000mL=0.0248 mol
x =0.052mol – 0.0248 mol=0.0272 mol
n (Et)eq = 0.034mol – 0.0272 mol= 6.8*10-3 mol
n (Es)eq =0.0272 mol
n (Water)eq = 0.247mol+ 0.0272 mol =0.2742 mol

Solution 7:
n (HAc)eq = 1mol/L*35.4 mL*1L/1000mL=0.0354 mol
x =0.070mol – 0.0354 mol=0.0346 mol
n (Et)eq = 0.017mol – 0.0346mol= -0.0176mol
n (Es)eq =0.0346 mol
n (Water)eq = 0.247mol+ 0.0346 mol =0.2816 mol
5. For solution 8:
CH3COOH + C2H5OH  CH3COOC2H5 + H2O
İ: M(HAc)0 Es(0) water (0)
E: M(HAc)0 + x x Es(0) - x water (0) - x

n (HAc)eq = M (NaOH) x V (titration)

x = n (HAc)eq - n (HAc)0
n (Et)eq = x
n (Es)eq = Es(0) - x
n (Water)eq = n (Water)0 - x
 M(NaOH) = 1.0M V(NaOH) = 20.8 mL n(HAc)eq=1mol/L x
0.0208 L=0.0208 mol
x=0.0208–0.017=3.80*10-3 mol
n(Et)eq=3.80*10-3mol
n (Es)eq= 0.041-3.80*10-3=0.0372 mol
n (Water)eq = 0.247-3.80*10-3= 0.2432 mol

 For solution 9:
CH3COOH + C2H5OH  CH3COOC2H5 + H2O
İ: Et(0) Es(0) water (0)
E: x Et(0) + x Es(0)-x water(0) -x

n (HAc)eq = M (NaOH) x V (titration)

x = n (HAc)eq = n(Et)eq- Et(0)
n (Et)eq = Et(0) + x
n (Es)eq = Es(0) - x
n (Water)eq = n (Water)0 – x

M(NaOH) = 1.0M V(NaOH) = 14.0 mL

n (HAc)eq = 1mol/L x 0.014L = 0.014 mol
x = 0.014 – 0 = 0.014mol
n (Et)eq =0.017+ 0.014=0.031 mol
n (Es)eq = 0.041 - 0.014= 0.027 mol
n (Water)eq = 0.247 - 0.014= 0.233 mol

6. K = [n(Es) * n(Water)] / [n(HAc) * n(Et)]

 Solution 1:
K=0.033*0.229/0.018*0.018=23.32
 Solution 2
K=0.015*0.343/0.016*0.016=20.10
 Solution 3:
K=7.10*10-3 *0.4011/0.0129*0.0129= 17.11
 Solution 4:
K=0.0048*0.2518/0.0122*0.0624=1.59
 Solution 5:
K=0.0174*0.2644/0.0336*0.0176=7.78
  Solution 6:
K=0.0272*0.2742/0.0248*6.8*10-3=44.23

 Solution 7:
K=0.0346*0.2816/0.0176*0.0354=15.64
 Solution 8:
K=0.0372 *0.2432/0.0038*0.0208=114.5
 Solution 9:
K=0.027*0.233/0.031*0.014=14.5
Since we obtain negative mole value in solution 7, we should
reject this data when we are calculating Kavg and standard
deviation.
Without reject solution 7 K value,
K(average)= 28.75
Standard deviation=34.25
By rejecting solution 7 K value, K(avg)=30.39
Standard deviation=36.24

Part 2. Heterogeneous Equilibria

1. For solution 1
n(I2)=n(I3-)=1/2*n(S2O3)=M(S2O3)*V(S2O3)
[I2]=n(I2)/V
 For aqeous phase:
n(I2)=n(I3-)=0.02mol/L*6.0x10-3L =1.2x10-4mol
[I2]= 1.2x10-4mol/0.05L=2.4x10-3M
 For organic phase:
n(I2)=n(I3-)=0.1mol/L*45.3x10-3L=4.53x10-3mol
[I2]= 4.53x10-3mol/0.025L=0.1812 M
KD=2.4x10-3M /0.1812 M =0.013 M

2. For solution 2 and 3

I2 + I-  I 3-

[I2](aq,eq) [I-]0 – x x
 [I2]aq,eq=KD*[I2]CHCl3

[I2]CHCl3=n(I2)/V=1/2*n(S2O32-)/VCHCl3=MS2O3*VS2O3/VCHCl3

n(I3-)aq,total=1/2xn(S2O32-)=M(S2O3)xV(S2O3)

[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

For solution 2:

For CHCl3 phase :

n(I2) =n(I3-)=1/2 *45.3mL*0.02 *10-3 L/mL=4.53*10-3 mol

[I2]CHCl3= 4.53*10-3 /0.025 =0.018 M

[I2]aq,eq=KD *0.018= 5.43*10-3 *0.018 =9.84*10-5M

[I2]aq,eq = [I3-] =9.84*10-5M

[I3-]aq,total=1/2 *11.8*10-3 *0.02/ 0.05 L=2.36*10-3 =[I3-] aq,eq +[I3-]

[I3-]aq,eq = 2.36*10-3 -9.84*10-5=2.26*10-3=x

[I-]eq =[I-]0 –x =0.01M -2.26*10-3=7.74*10-3

K = (2.26*10-3 )/(9.84*10-4)*7.74*10-3=296.74

For solution 3:

For CHCl3 phase :

n(I2) =n(I3-)=1/2*0.1*16.6 mL= 8.3*10-4mol

[I2]CHCl3= 8.3*10-4/0.025 =0.0332 M

[I2]aq,eq=KD *0.0332 = 5.43*10-3*0.0332 =1.8*10-4 M

[I2]aq,eq = [I3-]=1.8*10-4

[I3-]aq,total= 1/2* 0.02*60.5*10-3 /0.025 L =0.0242 M=[I3-] aq,eq +[I3-]

[I3-] aq,eq =0.0242-1.8*10-4=0.024 =x

[I-]eq =[I-]0 –x =0.1-0.024=0.076

K =(0.0242 ) /0.076*1.8*10-4=1769
 Questions

1) Reactants or products of an equilibrium is affected by certain conditions,

the position of the equilibrium shifts to the other side.[1]

2) Concentration, pressure and temperature affects the composition of an

equilibrium according to the Le Chateliers’s Principle.

3) A stress means that there is an outside effect to the equilibrium which can
be achieved by adding excess reactant or product or changing the temperature or
volume or pressure applying to the equilibrium. The equilibrium tries to create a
balance between reactants and products which will result in moving the change
to counteract position.

4) Concentration: The equilibrium will change its position according to the

excess concentration of products or reactants. If excess reactants added
equilibrium position changes to products to achieve balance.

Pressure : Only gas phase matters affected from pressure change. It is the
same logic as the concentration change.

Volume : Only gas phase matters affected from volume change. It is the same
logic as the concentration change.

Temperature: When the reaction is endothermic, temperature increase shifts

the equilibrium to reactants. When it is exothermic temperature increase
shifts the equilibrium to products.

5) Catalyst does not change the equilibrium constants. It speeds up the

reaction. In our experiment we used HCl for catalyst.

6) Only temperature affects the equilibrium constant.

Discussion

In this experiment we tried to determine the effects of varying concentrations

of homogenous and heterogeneous equilibrium. In the first part of the
experiment, we prepared 9 different solutions with different concentrations
which are esterification reactions. We prepared these solutions by adding excess
reactant or products and which created a stress for the equilibriums and as Le
Chateliers’s Principle states that the applied stress on the system will shift its
position to minimize the effect on the equilibrium. Therefore, the K values for
the reactions should be same, not affected by concentration change.
Nonetheless, every solution we study gives different equilibrium constants that
are not matching with theoretical results. Possible error sources might be:

Titration errors: Not reading the buret correctly, end point faults.

Volumetric errors: Not preparing the solutions in correct values by mistake.

Preparation time of the solutions: We prepared the mixtures one week ahead
and they might not reached the equilibrium.

In the second part of the experiment, we studied 3 different heterogeneous

mixtures, I2 distribution in organic and aqueous phases. Our purpose was
determining the equilibrium constant of the reactions. When we compared the
values there is a big difference in second and third mixtures might be caused by
separation error of the two phases or titration errors or volumetric errors. The
temperature of the surrounding is not achievable to keep constant; therefore it
might have distorted the K value.

Referance

[1] Atkins, P.W. (1993). The Elements of Physical Chemistry (3rd ed.). Oxford

University Press.