EXPERIMENT 4

THE
DETERMINATION
OF PARTIAL MOLAR
ENTHALPY

the enthalpy of a solution is a function of temperature. The partial molar enthalpy of mixing of a component is the heat change when one more of that component is added to a large volume of solution at a specific concentration. pressure and composition. Similar to the volume.INTRODUCTION A partial molar property is a thermodynamic quantity which indicates how an extensive property of a solution or mixture varies with changes in the molar composition of the mixture at constant temperature and pressure. . The excess molar enthalpy is identical with the molar enthalpy change on mixing and therefore is often termed as the heat of mixing.

so that nearly every constant-temperature chemical reaction is accompanied by energy and enthalpy changes. .INTRODUCTION The enthalpy of mixing is the enthalpy change associated with the dissolution of a substance in a solvent at constant pressure resulting in infinite dilution. It is most often expressed in kJ/mol at constant temperature. the reaction is called endothermic. the reaction is called exothermic. A chemical reaction involves the breaking of some chemical bonds and the formation of the other chemical bonds. If the system gives off heat when a reaction takes place at constant temperature. If the system absorbs heat at constant temperature. The breaking of bonds requires an input of energy and the formation of bonds gives off energy.

.INTRODUCTION In general. the value of a partial molar property of a constituent in a solution is not equal to the value for the pure substance.

. • To use the data to estimate the partial molar enthalpies of mixing or the two components in a mixture.OBJECTIVES • To determine the molar enthalpy of mixing (H) for the different mixtures of glycerol and water.

Add the specified volume of water through a buret them immediately cover the flask and mix the solution by swirling. Repeat the last four steps for all the specified mixtures of glycerol and water. Rinse and dry the Dewar flask thoroughly before continuing on a new measurement. Add the specified volume of water through a buret them immediately cover the flask and mix the solution by swirling.SCHEMATIC DIAGRAM Measure out the specified volume of glycerol into the Dewar flask through a pipet and allow it to equilibrate for two minutes before recording its constant temperature using a Fischer thermometer. For every minute. get the time temperature data and record the constant temperature obtained. . in three minutes.

126 0.01 8.021 .516 0.752 1. Composition of Glycerol.66 5 6 7 8 34.47 0.705 1.23 0.29 3.83 27.17 2.54 30.38 0.Water Mixtures No.85 67. mL mL Mol Mol glycero water glycero water l l (n1) (n2) 1 2 3 4 2.53 0.94 0.38 0.67 20.69 27.19 0.77 13.038 0.47 0.27 0.34 0.66 36.49 38.76 25.53 4.DATA Table 1.29 11.50 0.

CALCULATIONS Mole fraction of glycerol and water Where: X1=mole fraction of glycerol X2=mole fraction of water n1= mole of glycerol n2= mole of water .

5 J/K mol .CALCULATIONS Mean heat capacity : C(water) = 75.3 J/K mol : C(glycerol) = 207.

CALCULATIONS The molar enthalpy of mixing Where: ∆H= Molar Enthalpy C=Mean heat Capacity ∆T= Change in temperature .

662619 115.62619 7.010032 0.694737 0.Mole fraction of glycerol (X1) Mole fraction of water (X2) (J/K mol)  n1 n2 T (K) 0.13 2.941828 0.202128 0.4921 301.206349 0.6558 266.697368 0.899471 0.038 3.021 0.1 0.302632 0.989968 0.5 0.74 91.566 0.66 2.8668 0.793651 0.5 0.305263 0.4 212.23 1.52 79.34 0.47 0.38 1.2206 414.0083 141.5075 0.7 199.5 (J/mol) 76.3 0.75 0.4858 0.797872 0.5 0.668 0.47 1.8097 139.9 88.058172 0.29 0.19 1.9 101.5 0.8 167.100529 0.1 .3 180.7 0.53 0.

this is a possible equation: .CALCULATIONS • If you set the X1 in the general equation to zero. you can obtain this formula for H2: • For H1.

4575 266.8908 212.2139 414.8668421 114.5075 306.52 91.86350272 382.2 301.5218669 996.767 139.740267 79.3747368 88.07659574 424.7355206 2008.377 .4858 136.668 -377.8672844 2404.8668 262.662619 -562.CALCULATIONS H H1 H2 7.566 -216.1 27.1942422 7.0083 45.

mol fraction of glycerol (X1) and determine the value of H1 and H2 for a mixture of 0.7435 J/mol = H .55x + 73.991 y= 259.55 y= 261.CALCULATIONS • Draw a graph of the molar enthalpy of mixing (H) vs.55) + 73.55 (0. y = 259.991 :X1=.45 mol fraction of water.

CALCULATIONS .

CALCULATIONS H vs X1 3000 2500 2000 1500 H H2 H1 mixing 1000 500 0 0 1 2 3 4 -500 -1000 X1 5 6 7 8 9 .

We also had to make use of pure glycerol which was more viscous for the later part of the experiment because we ran out of the less viscous glycerol and that could be another reason for the discrepancy in the temperature of each mixture.DISCUSSIONS To simplify matters.6522 J/mol while its H2 is 1. the volumes for both glycerol and water had to be cut down to smaller portions and so we came up with the ones in the Table 1 since we knew that by doing so.03352x10-13 J/mol. The molar enthalpy of mixing at 0.7435 J/mol.45 mol fraction of water is 261. . the mole fractions for both would not be altered. Its H1 is481.

we learned that the temperature of glycerol and the temperature of the solution vary more visibly when the amount of glycerol is much greater than the amount of water in a mixture and makes the temperature of solution higher than that of the glycerol.CONCLUSION In this experiment. This also shows that the mixture of glycerol and water generally undergoes endothermic process because of the positive values that we obtained in our data. . All differences from the expected results can be accounted to the personal errors that we committed while performing the experiment when we did not maintain the consistency of the glycerol that we used and perhaps while adding the volumes of each substance into the Dewar flask.