EXPERIMENT 3

DETERMINATION OF PARTIAL MOLAR ENTHALPY

ABSTRACT

The enthalpy change when one mole of a component is added to a large volume of the

solution at a given concentration is called the partial molar enthalpy of mixing. This can be

obtained from the heat released or absorbed in a mixing process. In this laboratory

experiment, the molar enthalpy of mixing for different mixtures of glycerol and water was

determined through constant pressure calorimetry. The data obtained from this was used to

estimate the partial molar enthalpies of mixing of the two components in the mixture by

plotting the calculated molar enthalpy of mixing against the mole fraction of glycerol. The

partial molar enthalpy of mixing for glycerol and for water, 1615.58 J/mol and 231.98 J/mol

respectively, can be determined by drawing a tangent line at 0.20 mole fraction, which is

where the values are in unity.

INTRODUCTION

Partial molar quantities show how extensive properties of homogeneous mixtures

change with concentration as temperature, pressure, and the amount of all other species are

kept constant (DeVoe, 2015). In this experiment, we are interested in the partial molar

enthalpy of mixing. Partial molar enthalpy of mixing is defined as a change in enthalpy when

an infinitesimal amount of substance is added to a large volume of solution at a specific

concentration. A large volume is specified so that during the addition the volume or

concentration changes in solution are negligible (Beckett and Mckelvie, 1982).

The change in enthalpy at constant temperature and pressure associated with an

irreversible change of state, such as mixing, is equal to the heat exchanged between the

system and the surrounding (Ceder, 2001). Thus, the enthalpy of mixing at constant

temperature and pressure tells us how much heat will be released or absorbed when

combining chemical species. Enthalpy changes are measured in a constant -pressure

calorimeter. Enthalpies determined are usually reported as enthalpy change in mixing as a

function of mole fraction (Caermare, 2015).

The main objective of this experiment was to determine the enthalpy change in the

mixing phenomena for binary solutions. Using varying volumes of each component Water

and Glycerol paired in a set, the enthalpy associated is calculated and follows the following

mathematical relationship,

H= H (n1 , n2) (1)

where H = enthalpy of mixing, n1= no. of moles of component 1 (Glycerol),

n2= no. of moles of component 2 (Water).

 The partial molar volumes of H at a specified concentration are represented

through H 1 and H 2 , which is further defined by the partial derivative of H in

terms of n:

H 1= ( nH )
1 n2
H
(
and H 2= n2 )
n1
(2)

Relating to Equation (1),

d H= H 1 d n1 + H 2 d n 2 (3)

When integrated,

H=n1 H 1+n2 H 2 (4)

Dividing by the total number of moles,

H= X 1 H 1+ X 2 H 2 (5)

where H = molar enthalpy of mixing, X 2= mole fraction of component 2 (water),

and

X 1 = mole fraction of component 1 (glycerol).

Since X 1 + X 2 =1 , Equation 5 can be written as,

H= ( H 1 H 2 ) X 1 + H 2 (6)
Using the data obtained, the partial molar enthalpies of mixing of the two components in the

mixture were estimated by plotting the molar enthalpy of mixing against the mole fraction of

one of the components (Beckett and Mckelvie, 1982).

Partial molar quantities such as partial molar enthalpies are of central importance in

the study of solutions because they measure the variations of extensive thermodynamic

properties as chemical components are added or removed from the system (Ceder, 2001).

MATERIALS AND METHODS

Materials

The materials used to carry out the experiment were the following:

1. Coffee-cup calorimeter
This constant pressure calorimeter consists of two styrofoam cups nested and sealed with

a cover. Two holes were made on the cover to allow the use of a stirrer and a

thermometer.
2. Fischer thermometer

A Fischer thermometer was used to measure the temperature of the glycerol water

mixtures.

3. Stirrer
An improvised iron wire stirrer was used to mix glycerol and water inside the calorimeter.
4. Graduated cylinder

A graduated cylinder was used to measure specific volumes of water and glycerol for the

different mixtures.
5. Buret

A buret was used to store the pre-measured volumes of distilled water needed for the

mixtures.

6. Pipette
A pipette was used to measure the volume of glycerol and to transfer glycerol from its

reagent bottle to the calorimeter.

7. Timer

A cellular timer was used to monitor the time it took for the mixture to equilibriate and to

achieve constant temperature.

The software used for the calculation and tabulation of experimental data were Microsoft Excel

and GeoGebra 5.0.

Methods

The first part of the experiment was to measure the specified volumes of glycerol

(shown in Appendix A) and transfer it into the coffee-cup calorimeter. Each group was

assigned their respective mixtures. Only one group was able to use the Dewar flask since the

laboratory can only provide one. The glycerol was then allowed to equilibrate for two

minutes and its temperature was measured by the use of a Fischer thermometer. Next, a

corresponding amount of water was added into the coffee-cup calorimeter. After the addition

of water, the coffee-cup calorimeter was covered immediately and its contents were mixed

thoroughly by stirring and swirling. The temperature was measured and recorded for every

minute at a period of three minutes. All the steps were repeated for all the specified mixtures

in Appendix A. The time-temperature data for each mixture was presented to the class.

Using the Excel, the values for the mole fraction of glycerol (X 1) and water (X2), the

mean heat capacity of each set of mixture ( C ), the change in temperature (T), and the
molar enthalpy of mixing ( H ) were calculated and tabulated. The graph for the molar

enthalpy of each mixture ( H ) versus the mole fraction of glycerol (X1) was generated.

The equation of the tangent line was obtained by the analysis of the graph through GeoGebra.

The tangent line was added to the graph in Excel by substituting the values of the molar

fraction of glycerol to the equation of the tangent line (y = mx + b), generating the values for

y. Adding the values to the graph a curve with a tangent line through X=0.2 was generated.

After the generation of the tangent line, the values for H1 and H 2 were estimated

by using Equation (6) and relating it to y = mx + b and solving for the values manually. After

the generation of the tangent line, the values for H1 and H 2 were estimated by

using Equation (6) and relating it to y = mx + b and solving for the values manually.

RESULTS

Figure 1 shows the graph of the mole fraction of glycerol plotted against the molar enthalpy

of mixing. The graph shows that the values do not show a linear relationship and varies

throughout the volume sets.

 H vs X1

f(x) = 1383.6x + 231.98

R = 1

Molar Enthalpy of Mixing (H)

f(x) = - 36.4x + 289.45

R = 0
0.05 0.15 0.25 0.35 0.45 0.55 0.65 0.75 0.85 0.95
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Mole Fraction of Glycerol (X1)

Figure 1. Graphical representation of enthalpy of mixture as a function of mole fraction of glycerol with corresponding
graphical representations of the tangent line and its components ( H1 and H2 ) and the corresponding line
equations.

Figure 2 shows the mole fraction of glycerol plotted against the molar enthalpy of mixing

with the corresponding tangent line.

 100
0
-100 0.05 0.15 0.25 0.35 0.45 0.55 0.65 0.75 0.85 0.95
-2000 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
-300 f(x) = 36.4x
- 1383.6x - 231.98
- 289.45
-400 R = 1 0
Tan line -500 (Tan line)
Linear dh2 dh1 Curve
-600
-700
Molar Enthalpy of Mixing (H)
-800
-900
-1000
-1100
-1200
Linear (Curve)
-1300
-1400
-1500
-1600

Mole Fraction of Glycerol (X1)

Figure 2. Graphical representation of enthalpy of mixture as a function of mole fraction of glycerol with corresponding
graphical representations of the tangent line and its components ( H1 and H2 ) and the corresponding line
equations depicting an exothermic process.

DISCUSSION

In this experiment the enthalpy change was measured calorimetrically by monitoring

the temperature change of the contents at constant pressure. Series of calculations were made

for us to determine the values of the molar enthalpy of mixing and the partial molar

enthalpies. These calculations include the number of moles of water and glycerol, mole

fractions, change in temperature and mean heat capacity of the mixture.

The molar enthalpy of mixing of a mixture can be determined using the change in

temperature of the mixture and the heat capacities of the components of the mixture. Based

on the results, it can be observed that the mean heat capacity of the mixtures increases as the

mole fraction of glycerol increases. This outcome is reasonable because the mean heat
capacity of each mixture is the weighted average of the heat capacity of each component

multiplied with the mole fraction.

From Figure 1, it can be observed that the graph did not follow linearity since the

partial molar enthalpies of mixing differ with the concentrations of the components. Dilute

components of the mixture are having interactions with the concentrated ones hence the

partial molar properties of the components will differ significantly from the pure substance.

The tangent line was graphed to estimate the partial molar enthalpies of the two

components of the binary solution. By graphing the tangent line at X 1=0.2, the values for

H1 and H 2 were solved with high mathematical certainty and was found to be

H 1= 1615.58 J K-1 mol-1 and H 2= 231.98 J K-1 mol-1.

The values of H 1 and H 2 were verified in Appendix B by substituting X1= 0

to solve for the value of H2 and H1 . The results were found to be H= H 2

and H = H 1 respectively.

Further research and analysis of the data suggested that the graph should exhibit that

of an exothermic reaction so the values of H were supposed to be negative. The graph

was corrected as shown in Figure 2.

Using GeoGebra, the tangent line was regenerated and was found out to have an

equation of y = -1383.6x 231.98.

 An error is also present in the values of the H1 and H 2 , so they were

recalculated. The recalculation resulted to H 1=1615.58 and H 2=231.98 . The

negative values tell us that the process was exothermic.

CONCLUSION

Through this experiment, the experimenters were able to calculate and estimate values

of the heat capacities, and molar enthalpy of mixing of each set of volumes of Glycerol and

Water using the Coffee-Cup Calorimeter. Based on the outcome of the calculated values and

the graph, its concluded that this experiment was successfully executed.

In this experiment, we have learned that the extent of change in temperature of the

mixtures is dependent on the extensive properties of the solution and that constant-pressure

calorimetry is a method that can be used to measure changes in enthalpy. Errors of the

experiment can be accounted to personal errors such as failure to maintain consistency in

adding the specified volumes for each substance, mixing and reading of temperatures. It is

also more efficient to use a Dewar flask instead of an improvised coffee-cup calorimeter.

REFERENCES

[1] Beckett, R & McKelvie, I., Chemistry Practical Manual., Chrisholm Institute of

Technology (C.I.T), 1982.

[2] DeVoe, H., Thermodynamics and Chemistry, 2nd ed., Howard DeVoe, 2015.

[3] Mortimer, R., Physical Chemistry, 3rd ed., Elsevier Inc., 2008.

[4] Atkins, P & De Paula, J, Physical Chemistry, 9th ed., Oxford University Press, 2010.
[5] Hernandez, A.; docslide.us/documents/the-determination-of-partial-molar-enthalpy.html

(accessed October 22,2016)

[6] Caermarc, C.A., Determination of Partial Molar Enthalpy of Glycerol Water Mixtures,

College of Science and Mathematics, Western Mindanao State University

[7] Ceder.; https://ocw.mit.edu/courses/materials-science-and-engineering/3-20-materials-at-

equilibrium-sma-5111-fall-2003/study-materials/mixtures.pdf (accessed October 22, 2016)

[8] Gaje, Arnold. Physical Chemistry Lab Manual; Chemistry Department: University of the

Philippines Visayas Miagao, Iloilo, 2016, Experiment 3.

APPENDICES

Appendix A Tables

Table 1. Composition of Glycerol-Water

Mixtures
N mL mL # mol # mol

o Glycerol Water Glycerol Water

. (n1) (n2)
1 7.3 178.0 0.1 9.9
2 36.5 81.0 1.0 9.0
3 73.0 72.0 1.0 4.0
4 55.0 31.5 0.75 1.75
5 91.0 22.5 1.25 1.25
6 102.0 11.0 1.4 0.6
7 97.0 6.0 1.33 0.33
8 66.0 1.0 0.9 0.1

Table 2. Heat Capacities of Glycerol and Water

C J/K-mol
Water 75.3
Glycerol 207.5
Table 3. Experimental Molar Enthalpy of Mixing ( H
J J
C( ) H( )
K mol mol
X1 Glycerol X2 Water n1 n2 T (K)
0.01 0.99 0.1 9.9 0.5 76.622 38.311
0.1 0.9 1 9 2 88.52 177.04
0.2 0.8 1 4 5 101.74 508.7
0.3 0.7 0.75 1.75 4.2 114.96 482.832
0.5 0.5 1.25 1.25 2 141.4 282.8
0.7 0.3 1.4 0.6 2 167.84 335.68
0.8012048 0.1987952 1.33 0.33 2 181.2193 362.4386
0.9 0.1 0.9 0.1 0 194.28 0

Table 4. Tabulation of Trial and Constant Temperature Data

Constant Constant Temperature Trial Temperature

Temperature Obtained tf Readings

of Glycerol ti
28.0

28 28.5 28.5

28.5
31.5

30 32 32

32
35

31 36 36

36
33.5

29.5 33.7 33.7

33.7
31.9

30 32 32.0
 32.0
34

32 34 34

34
32

30 32 32

32
33

33 33 33

33

Table 5. Molar Enthalpy of Mixing Experimental Values

C( J K1 mol1 )
H 508.7
H1 1615.58
H2 231.98

Appendix B Calculations

Mole Fraction of Glycerol:

( Moles of component )
X 1=
(Total moles of all components)
Mixture 1 Mixture 2 Mixture 3 Mixture 4

n1 n1 n1 n1
X 1= X 1= X 1= X 1=
( n1 + n2 ) (n1+ n2 ) ( n1+ n2 ) (n1+ n2 )

0.1 1.0 1.0 0.75

X 1= X 1= X 1= X 1=
(0.1+ 9.9) (1.0+ 9.0) (1.0+ 4.0) (0.75+1.75)

X 1=0.01 X 1=0.1 X 1=0.2 X 1=0.3

Mixture 5 Mixture 6 Mixture 7 Mixture 8

n1 n1 n1 n1
X 1= X 1= X 1= X 1=
( n1 + n2 ) (n1+ n2 ) ( n1+ n2 ) (n1+ n2 )

1.25 1.4 1.33 0.9

X 1= X 1= X 1= X 1=
(1.25+ 1.25) (1.4 +0.6) (1.33+ 0.33) ( 0.9+0.1)

X 1=0.5 X 1=0.7 X 1=0.8012048 X 1=0.9

Mole Fraction of Water:

( Moles of component )
X 2=
( Total moles of all components)

Mixture 1 Mixture 2 Mixture 3 Mixture 4

n2 n2 n2 n2
X 2= X 2= X 2= X 2=
( n2 +n1 ) ( n2 +n1 ) (n2 +n1 ) ( n2 +n1 )

0.99 9.0+1.0 4.0 1.75

X 2= X 2= X 2=
( 0.99+0.1) 9.0 ( 4.0+1.0) ( 1.75+ 0.75)
X 2=

X 2=0.9 9 X 2=0.8 X 2=0.7

X 2=0.9
Mixture 5 Mixture 6 Mixture 7 Mixture 8

n2 n2 n2 n2
X 2= X 2= X 2= X 2=
( n2 +n1 ) ( n2 +n1 ) (n2 +n1 ) ( n2 +n1 )

1.25 0.6 0.33 0.1

X 2= X 2= X 2= X 2=
(1.25+ 1.25) ( 0.6+1.4) (0.33+1.33) (0.1+ 0.9)

X 2=0.5 X 2=0.3 X 2=0.1987952 X 2=0.1

Mean Heat Capacity of each Mixture:

C=X 1 C(Glycerol ) + X 2 C(Water)

Mixture 1 Mixture 2

C=X 1 C(Glycerol ) + X 2 C(Water) C=X 1 C(Glycerol ) + X 2 C(Water)

C=(0.01)(207.5)+(0.99)(75.3) C=(0.1)(207.5)+(0.9)(75.3)

C=2.075+74.547 C=20.75+67.77

J J
C=76.622( ) C=88.52( )
K mol K mol

Mixture 3 Mixture 4

C=X 1 C(Glycerol ) + X 2 C(Water) C=X 1 C(Glycerol ) + X 2 C(Water)

C=(0.2)(207.5)+(0.8)(75.3) C=(0.3)(207.5)+( 0.7)(75.3)

C=41.5+60.24 C=62.25+52.71

J J
C=101.74( ) C=114.96( )
K mol K mol

Mixture 5 Mixture 6
 C=X 1 C(Glycerol ) + X 2 C(Water) C=X 1 C(Glycerol ) + X 2 C(Water)

C=(0.5)(207.5)+(0.5)(75.3) C=(0.7)( 207.5)+(0.3)(75.3)

C=103.75+37.65 C=145.25+22.59

J J
C=141.4( ) C=167.84( )
K mol K mol

Mixture 7 Mixture 8

C=X 1 C(Glycerol ) + X 2 C(Water) C=X 1 C(Glycerol ) + X 2 C(Water)

C=(0.8012048)(207.5)+(0.1987952)(75.3) C=(0.9)(207.5)+( 0.1)(75.3)

C=166.249996+14.96927856 C=186.75+7.53

J J
C=181.2193( ) C=194.28( )
K mol K mol

Change in Temperature of each Mixture:

T =T f T i

Mixture 1 Mixture 2

T =T f T i T =T f T i

T =28.528 T =3230

T = 0.5 K T = 2 K

Mixture 3 Mixture 4

T =T f T i T =T f T i

T =3631 T =33.729.5
 T = 5 K T = 4.2 K

Mixture 5 Mixture 6

T =T f T i T =T f T i

T =3230 T =3432

T = 2 K T = 2 K
Mixture 7 Mixture 8

T =T f T i T =T f T i

T =3230 T =3333

T = 2 K T = 0 K

Molar Enthalpy of Mixing of each Mixture:

H=C T

Mixture 1 Mixture 2

H=C T H=C T

H=(76.622) (0.5) H=(88.52) ( 2)

J J
H=38.311 H=177.04
mol mol

Mixture 3 Mixture 4

H=C T H=C T

H=(101.74) (5) H=(114.96) (4.2)

 J J
H=508.7 H=482.832
mol mol

Mixture 5 Mixture 6

H=C T H=C T

H=(141.4) (2) H=(167.84) (2)

J J
H=282.8 H=335.68
mol mol

Mixture 7 Mixture 8

H=C T H=C T

H=(181.2193) (2) H=(194.28) (0)

J J
H=362.4386 H=0
mol mol

1. Compute for the mole fraction of glycerol (X1) and water (X2).

n1 n2
X 1= X 2=
( n1 + n2 ) ( n2 +n1 )

0.9 0.1
X 1 (no . 8)= X 1 (no . 8)=
0.9+0.1 0.1+0.9

X 1 (no . 8)=0.9 X 2 (no . 8)=0.1

2. Given that the heat capacities of water and glycerol, tabulated in Table 5. Estimate the

following:
a. C
C(no .8)= X 1 C (Glycerol ) +X 2 C(Water)
 C(no .8)=(0.9)(207.5)+(0.1)(75.3)

C(no .8)=186.75+ 7.53

J
C(no .8)=194.28( )
K mol

b. H

H ( no. 8)=C (no .8 ) T ( no.8 )

H ( no. 8)=194.28 x 0

J
H ( no. 8)=0
mol

Change in Temperature

T (no .8 )=T f (no.8 )

T i
( no.8 )

T (no .8 )=33.033.0

T (no .8 )=0 K

Note: Although the calculations were originally done in excel, the general formulas used were

still as written above. Furthermore, the complete tabulation of the calculated mole fraction of

water and glycerol, the mean heat capacity, the change in temperature and the molar enthalpy

of mixing can be found in Table 2.

Equationof the tangent line :

y=1383.6 x +231.98 y=mx +b

 H= ( H 1 H 2 ) X 1+ H 2

Find H 1 @ X 1=0.2, H=508.7

m=( H 1 H 2 )

1383.6= H 1231.98

H 1=1383.6+ 231.98

H 1=1615.58

Tangent Line (Correction):

y=1383.6 x231.98

Find H 1 @ X 1=0.2, H=508.7

m=( H 1 H 2 )

1383.6= H 1(231.98)

H 1=(1383.6 +231.98)

H 1=1615.58

H 2=231.98

Verification of the values of ( H 1 H 2 ) when X1 = 0 and X1 = 1:

 H= ( H 1 H 2 ) X 1+ H 2

@ X1 = 0

H= ( H 1 H 2 ) (0)+ H 2

H=0+ H 2

H= H 2

@ X1 = 1

H= ( H 1 H 2 ) (1)+ H 2

H= ( H 1 H 2 ) + H 2

H= H 1