APPENDIX C

COMPUTATION

A. Preparation of Solutions
1. Preparation of 0.1 M HCl:
𝑉1 𝐶1 = 𝑉2 𝐶2
(500 𝑚𝐿)(0.1𝑀) = 𝑉2 (12 𝑀)
𝑽𝟏 = 𝟒. 𝟐 𝒎𝑳

2. Preparation of 0.1 M NaOH:

𝑤𝑡
𝑀 = 𝑀𝑊 (𝐿
𝑠𝑜𝑙′ 𝑛 )

𝑚𝑜𝑙 𝑤𝑡
0.1 = 𝑔
𝐿 40 (1 𝐿)
𝑚𝑜𝑙

𝑤𝑡𝑁𝑎𝑂𝐻 = 4 𝑔
*Standardization of the NaOH solution:
𝑚𝑒𝑞𝐾𝐻𝑃 = 𝑚𝑒𝑞𝑁𝑎𝑂𝐻
1000𝑚𝐿
𝑤𝑡(𝑓)( )
1𝐿
= 𝑉𝑁𝑎𝑂𝐻 𝑁𝑁𝑎𝑂𝐻
𝑀𝑊
𝑒𝑞 1000𝑚𝐿
𝑤𝑡(1 )( ) 𝑚𝑜𝑙 𝑒𝑞
𝑚𝑜𝑙 1𝐿
𝑔 = (10 𝑚𝐿)(0.1 )(1 𝑚𝑜𝑙)
204.22 𝐿
𝑚𝑜𝑙

𝑤𝑡 = 0.20 𝑔
 Trial 1: V = 10.4 mL
𝑒𝑞 1000𝑚𝐿
(0.20 𝑔)(1 )( ) 𝑒𝑞
𝑚𝑜𝑙 1𝐿
𝑔 = (10.4 𝑚𝐿)(𝑀𝑁𝑎𝑂𝐻 )(1 )
204.22 𝑚𝑜𝑙
𝑚𝑜𝑙

𝑀𝑁𝑎𝑂𝐻 = 0.0942 𝑀
 Trial 2: V = 10.2 mL
𝑒𝑞 1000𝑚𝐿
(0.20 𝑔)(1 )( ) 𝑒𝑞
𝑚𝑜𝑙 1𝐿
𝑔 = (10.2 𝑚𝐿)(𝑀𝑁𝑎𝑂𝐻 )(1 𝑚𝑜𝑙 )
204.22
𝑚𝑜𝑙

𝑀𝑁𝑎𝑂𝐻 = 0.0960 𝑀
 𝟎.𝟎𝟗𝟒𝟐+𝟎.𝟎𝟗𝟔𝟎
𝑪𝒂𝒗𝒆 = = 𝟎. 𝟎𝟗𝟓𝟏 𝑴
𝟐

3. Preparation of 0.1 M Ethyl Acetate:

𝑤𝑡 𝜌(𝑣)
𝑀 = 𝑀𝑊 (𝐿 =
𝑠𝑜𝑙′ 𝑛 ) 𝑀𝑊 (𝐿𝑠𝑜𝑙′ 𝑛 )

𝑔
𝑚𝑜𝑙 0.902 (𝑉)
𝑚𝐿
0.1 = 𝑔
𝐿 88.11 (1 𝐿)
𝑚𝑜𝑙

𝑉 = 9.7683 𝑚𝐿 ; 𝑉𝑎𝑐𝑡𝑢𝑎𝑙 = 9.8 𝑚𝐿

(0.0951 N)(10.9 mL)
𝐶1 = = 0.1037 𝑀
(10 mL)

(0.0951 N)(10.7 mL)

𝐶2 = = 0.1018 𝑀
(10 mL)

𝟎.𝟏𝟎𝟑𝟕+𝟎.𝟏𝟎𝟏𝟖
𝑪𝒂𝒗𝒆 = = 𝟎. 𝟏𝟎𝟐𝟖 𝑴
𝟐

B. Saponification Reaction

NaOH EtAc NaAc EtOH

I CAO CBO 0 0

C - (CAO - CA) - (CAO - CA) CAO - CA CAO - CA

E CA CB CAO - CA CAO - CA

Note: 0.0986 N NaOH is used as titrant; 0.0951 N NaOH is used in saponification

*For Variation 1:1 ratio
@ initial:
𝑉𝑁𝑎𝑂𝐻 = 50 𝑚𝐿 (0.0951 M)
𝑉𝐸𝐴 = 50 𝑚𝐿 (0.1003 M)
(0.0951 𝑀)(0.050 𝐿)
𝐶𝑁𝑎𝑂𝐻 = = 0.04755 𝑀
0.1 𝐿
 (0.1003 𝑀)(0.050 𝐿)
𝐶𝐸𝐴 = = 0.05015 𝑀
0.1 𝐿
CB0 0.05015
= = 𝟏. 𝟎𝟓𝟒𝟕
CA0 0.04755

Trial 1

Unreacted HCl with excess NaOH in the mixture/HCl reacted with NaOH titrant:
(.0986 N)(10.4mL)
V1 = = 𝟗. 𝟗𝟕𝟓𝟏 𝐦L
(.1028N)

HCl reacted with unreacted NaOH (saponification):

V= 10 - 9.9751 = 0.0249 mL

.1028 N
nHCl = (0.0249 mL)( 1000 mL) = 2.5597 x 𝟏𝟎−𝟔 mol = nNaOH unreacted
2.5597 x 10−6 mol
Munreacted NaOH = = 𝟐. 𝟓𝟓𝟗𝟕 𝐱 𝟏𝟎−𝟓 𝐦𝐨𝐥 /L
0.1 L

@ equilibrium:

CNaOH = .04755 M – x = 𝟐. 𝟓𝟓𝟗𝟕 𝐱 𝟏𝟎−𝟓 𝐦𝐨𝐥 /L

x = 0.0475 M = CNaAc = CEtOH
CEtAc = .05015 M - 0.0475 M = 0.00265 M

Second-order reaction following elementary rate law:

dCA
- = kCA CB
dt

dCA
- = kCA (CB0 − CA0 + CA )
dt

dCA
- = kCA (1.0547CA0 − CA0 + CA )
dt

dCA
- = kCA (0.0547CA0 + CA )
dt

dCA
- = kdt
CA (0.0547CA0 + CA )

dCA dCA
+ = -kdt
CA 0.0547CA0 + CA
Integrating with limits from CA0 to CA:

1 0.0547CA0 + CA 1 CA
ln - ln = k(20)
0.0547CA0 0.0547CA0 + CA0 0.0547CA0 CA0

k = 97.4335 L/mol-min

For KC:

C C (0.0475 M)(0.0475 M)
Kc = CNaAc CEtOH = (2.5597 x 10−5 )(0.00265 M) = 𝟑𝟑𝟐𝟔𝟐. 𝟑𝟎𝟎𝟏
NaOH EtAc

Trial 2

Unreacted HCl with excess NaOH in the mixture/HCl reacted with NaOH titrant:
(.0986 N)(10.3mL)
V2 = = 𝟗. 𝟖𝟕𝟗𝟐 𝐦L
(.1028N)

HCl reacted with unreacted NaOH (saponification):

V= 10 - 9.8792 = 0.1208 mL

.1028 N
nHCl = (0.1208 mL)( 1000 mL) = 1.2418 x 𝟏𝟎−𝟓 mol = nNaOH unreacted
1.2418 x 10−5 mol
Munreacted NaOH = = 𝟏. 𝟐𝟒𝟏𝟖 𝐱 𝟏𝟎−𝟒 𝐦𝐨𝐥 /L
0.1 L

@ equilibrium:

CNaOH = .04755 M – x = 𝟏. 𝟐𝟒𝟏𝟖 𝐱 𝟏𝟎−𝟒 𝐦𝐨𝐥 /L

x = 0.0474 M = CNaAc = CEtOH
CEtAc = .05015 M - 0.0474 M = 0.00275 M

Second-order reaction following elementary rate law:

1 0.0547CA0 + CA 1 CA
ln - ln =k(20)
0.0547CA0 0.0547CA0 + CA0 0.0547CA0 CA0

k = 115.9481 L/mol-min

For KC:

C C (0.0474 M)(0.0474 M)
Kc = CNaAc CEtOH = (1.2418 x 10−4 )(0.00275 M) = 𝟔𝟓𝟕𝟗. 𝟏𝟖𝟖𝟔
NaOH EtAc
 97.4335+115.9481
Ave k = = 106.6908
2

33262.3001+6579.1886
Ave K = = 𝟏𝟗𝟗𝟐𝟎. 𝟕𝟒𝟒𝟒
2

*For Variation 1:2 ratio

@ initial:
𝑉𝑁𝑎𝑂𝐻 = 25 𝑚𝐿 (0.0951 M)
𝑉𝐸𝐴 = 50 𝑚𝐿 (0.1003 M)
(0.0951 𝑀)(0.025 𝐿)
𝐶𝑁𝑎𝑂𝐻 = = 0.0317 𝑀
0.075 𝐿

(0.1003 𝑀)(0.050 𝐿)
𝐶𝐸𝐴 = = 0.0669 𝑀
0.075 𝐿
CB0 0.0669
= = 2.1104
CA0 0.0317

Trial 1

Unreacted HCl with excess NaOH in the mixture/HCl reacted with NaOH titrant:
(.0986 N)(7.4mL)
V1 = = 𝟕. 𝟎𝟗𝟕𝟕 𝐦L
(.1028N)

HCl reacted with unreacted NaOH (saponification):

V= 10 – 7.0977 = 2.9023 mL

.1028 N
nHCl = (2.9023 mL)( 1000 mL) = 2.9842 x 𝟏𝟎−𝟒 mol = nNaOH unreacted
2.9842 x 10−4 mol
Munreacted NaOH = = 𝟑. 𝟗𝟕𝟖𝟗 𝐱 𝟏𝟎−𝟑 𝐦𝐨𝐥 /L
0.075 L

@ equilibrium:

CNaOH = .0317 M – x = 𝟑. 𝟗𝟕𝟖𝟗 𝐱 𝟏𝟎−𝟑 𝐦𝐨𝐥 /L

x = 0.0277 M = CNaAc = CEtOH
CEtAc = .0669 M - 0.0277 M = 0.0392 M

Second-order reaction following elementary rate law:

dCA
- =kCA CB
dt
 dCA
- =kCA (CB0 − CA0 + CA )
dt

dCA
- =kCA (2.1104CA0 − CA0 + CA )
dt

dCA
- =kCA (1.1104CA0 + CA )
dt

dCA
- =kdt
CA (1.1104CA0 + CA )

dCA dCA
+ = -kdt
CA 1.1104CA0 + CA

Integrating with limits from CA0 to CA:

1 1.1104CA0 + CA 1 CA
ln - ln =k(20)
1.1104CA0 1.1104CA0 + CA0 1.1104CA0 CA0

k = 14.3091 L/mol-min

For KC:

C C (0.0277 M)(0.0277 M)
Kc = CNaAc CEtOH = (3.9789 x 10−3 )(0.0392 M) = 𝟒. 𝟗𝟏𝟗𝟒
NaOH EtAc

Trial 2

Unreacted HCl with excess NaOH in the mixture/HCl reacted with NaOH titrant:
(.0986 N)(7.9mL)
V2 = = 𝟕. 𝟓𝟕𝟕𝟐 𝐦L
(.1028N)

HCl reacted with unreacted NaOH (saponification):

V= 10 – 7.5772 = 2.4228 mL

.1028 N
nHCl = (2.4228 mL)( 1000 mL) = 2.4906 x 𝟏𝟎−𝟒 mol = nNaOH unreacted
2.4906 x 10−4 mol
Munreacted NaOH = = 𝟑. 𝟑𝟐𝟎𝟖 𝐱 𝟏𝟎−𝟑 𝐦𝐨𝐥 /L
0.075 L

@equilibrium:

CNaOH = .0317 M – x = 𝟑. 𝟑𝟐𝟎𝟖 𝐱 𝟏𝟎−𝟑 𝐦𝐨𝐥 /L

x = 0.0284 M = CNaAc = CEtOH
CEtAc = .0669 M - 0.0284 M = 0.0385 M
Second-order reaction following elementary rate law:

1 1.1104CA0 + CA 1 CA
ln - ln =k(20)
1.1104CA0 1.1104CA0 + CA0 1.1104CA0 CA0

k = 24.4813 L/mol-min

For KC:

C C (0.0284 M)(0.0284 M)
Kc = CNaAc CEtOH = (3.3208 x 10−3 )(0.0385M) = 𝟔. 𝟑𝟎𝟖𝟔
NaOH EtAc

14.3091+24.4813
Ave k = = 19.3952 L/mol-min
2

4.9194 +6.3086
Ave K = = 𝟓. 𝟔𝟏𝟒
2

*For Variation 2:1 ratio

@ initial:
𝑉𝑁𝑎𝑂𝐻 = 50 𝑚𝐿 (0.0951 M)
𝑉𝐸𝐴 = 25 𝑚𝐿 (0.1003 M)
(0.0951 𝑀)(0.05 𝐿)
𝐶𝑁𝑎𝑂𝐻 = = 0.0634 𝑀
0.075 𝐿
(0.1003 𝑀)(0.025 𝐿)
𝐶𝐸𝐴 = = 0.0334 𝑀
0.075 𝐿
CA0 0.0634
= = 𝟏. 𝟖𝟗𝟖𝟐
CB0 0.0334

Trial 1

Unreacted HCl with excess NaOH in the mixture/HCl reacted with NaOH titrant:

(.0986 N)(9.9mL)
V1 = = 𝟗. 𝟒𝟗𝟓𝟓 𝐦L
(.1028N)

HCl reacted with unreacted NaOH (saponification):

V= 10 – 9.4955 = 0.5045 mL

.1028 N
nHCl = (0.5045 mL)( 1000 mL) = 5.1863 x 𝟏𝟎−𝟓 mol = nNaOH unreacted
5.1863 x 10−5 mol
Munreacted NaOH = = 𝟔. 𝟗𝟏𝟓𝟏 𝐱 𝟏𝟎−𝟒 𝐦𝐨𝐥 /L
0.075 L

@ equilibrium:

CNaOH = .0634 M – x = 𝟔. 𝟗𝟏𝟓𝟏 𝐱 𝟏𝟎−𝟒 𝐦𝐨𝐥 /L

x = 0.0627 M = CNaAc = CEtOH
CEtAc = .0334 M - 0.0627 M = -0.0293 M = 0
Second-order reaction following elementary rate law:

dCA
- =kCA CB
dt

dCA dCB
- =-
dt dt

dCB
- = kCA CB
dt

dCB
- =kCB (CA0 − CB0 + CB )
dt

dCB
- =kCB (1.8982CB0 − CB0 + CB )
dt

dCB
- =kCB (0.8982CB0 + CB )
dt

dCB
- =kdt
CB (0.8982CB0 + CB )

dCB dCB
+ = -kdt
CB 0.8982CB0 + CB

Integrating with limits from CB0 to CB:

1 0.8982CB0 + CB 1 CB
ln - ln =k(20)
0.8982CB0 0.8982CB0 + CB0 0.8982CB0 CB0

k = infinity
For KC:

C C (0.0627 M)(0.0627 M)
Kc = CNaAc CEtOH = (6.9151 x 10−4 M)(0 M) = 𝐢𝐧𝐟𝐢𝐧𝐢𝐭𝐲
NaOH EtAc

Trial 2

Unreacted HCl with excess NaOH in the mixture/HCl reacted with NaOH titrant:
(.0986 N)(10.4mL)
V2 = = 𝟗. 𝟗𝟕𝟓𝟏 𝐦L
(.1028N)

HCl reacted with unreacted NaOH (saponification):

V= 10 – 9.9751 = 0.0249 mL

.1028 N
nHCl = (0.0249 mL)( 1000 mL) = 2.5597 x 𝟏𝟎−𝟔 mol = nNaOH unreacted
2.5597 x 10−6 mol
Munreacted NaOH = = 𝟑. 𝟒𝟏𝟐𝟗 𝐱 𝟏𝟎−𝟓 𝐦𝐨𝐥 /L
0.075 L

@ equilibrium:

CNaOH = .0634 M – x = 𝟑. 𝟒𝟏𝟐𝟗 𝐱 𝟏𝟎−𝟓 𝐦𝐨𝐥 /L

x = 0.0634 M = CNaAc = CEtOH
CEtAc = .0334 M - 0.0634 M = -0.03 M = 0

Second-order reaction following elementary rate law:

1 0.8982CB0 + CB 1 CB
ln - ln =k(20)
0.8982CB0 0.8982CB0 + CB0 0.8982CB0 CB0

k = infinity

For KC:

C C (0.0634 M)(0.0634 M)
Kc = CNaAc CEtOH = (3.4129 x 10−5 M)(0 M) = 𝐢𝐧𝐟𝐢𝐧𝐢𝐭𝐲
NaOH EtAc

Ave k = 𝐢𝐧𝐟𝐢𝐧𝐢𝐭𝐲

Ave K = 𝐢𝐧𝐟𝐢𝐧𝐢𝐭𝐲