CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

Enthalpy change of mixing

Marks:
Experiment done on: 01/02/2018

100

Report submitted on: 08/02/2018

For Instructors use only:

No Section Max. Marks Marks

1 Introduction / background theory -

2 Experimental details: materials and methods -

3 Experimental observations; Raw data 20

4 Sample calculations 20

5 Results, discussion and conclusions 40

7 Suggestions for improvement 10

8 Overall formatting & References 10

Total 100

Batch: B
Group: B11

Name (in alphabetical order) Roll Number

Dhruvi Shah CH17B116

Harshit Jindal CH17B112

Neeraj Jadhavar CH17B113

Pranav Pendharkar CH17B115

 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

Introduction and Background theory

Aim

Enthalpy change of mixing.

 To Calculate thermal capacity of flask, specific heat of mixture and enthalpy change of mixing using the
corresponding temperature changes.
 To determine Temperature change for water & alcohol mix, temperature change after mixing, temperature change
for mixture of water and alcohol for different compositions
 Fit Δh𝑚𝑖𝑥/(X1X2) vs 𝑥1 as a polynomial
 Calculate Δh𝑚𝑖𝑥 using the fitted coefficients and compare with experimental data
 Compare Δh𝑚𝑖𝑥 with literature data
 Calculate relative partial molar enthalpy analytically using the equation
dΔhmix
̅1 − h1 = Δhmix − x2 ∗ (
h )
𝑑𝑋2
Similarly, for h̅2 − h2

Theory

Partial molar properties are the thermodynamic properties which vary with the molar composition of the components.
It helps us to understand:

 Properties of components in a mixture

 Dominating forces(cohesive/adhesive)
 Heat of mixing: The amount of heat exchanged when two components are mixed

When solids, liquids or gases are combined, the thermodynamic quantities of the system experience a change as a result
of the mixing.
A solution is created when two or more components mix homogeneously to form a single phase. Studying solutions is
important because most chemical and biological life processes occur in systems with multiple components. Understanding
the thermodynamic behaviour of mixtures is integral to the study of any system involving either ideal or non-ideal solutions
because it provides valuable information on the molecular properties of the system.

Introduction

Enthalpy of Solution

A solution is a homogeneous mixture of two or more substances and can either be in the gas phase, the liquid phase, the
solid phase. The enthalpy change of solution refers to the amount of heat that is released or absorbed during the
dissolution process (at constant pressure). This enthalpy of solution (ΔHsolution) can either be positive (endothermic) or
negative (exothermic). When understanding the enthalpy of solution, it is easiest to think of a hypothetical three-step
process happening between two substances. One substance is the solute, let’s call that A. The other substance is the
solvent, let’s call that B.

Step 1: Breaking up the Solute

The first process that happens deals only with the solute, A, which requires breaking all intramolecular forces holding it
together. This means the solute molecules separate from each other. The enthalpy of this process is called ΔH1. This since
this is always an endothermic process (requiring energy to break interactions), then ΔH 1>0.

Step 2: Breaking up the Solvent

Much like how the solute, A, needed to break apart from itself, the solvent, B, also needs to overcome the intermolecular
forces holding it together. This causes the solvent molecules separate from each other. The enthalpy of this process is
called ΔH2. Like the first step, this reaction is always endothermic (ΔH 2>0) because energy is required to break the
interaction between the B molecules.
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

Step 3: Combining the Two Together

The third process is when substance A and substance B mix to for a solution. The separated solute molecules and the
separated solvent molecules join together to form a solution. This solution will contain one mole of the solute A in an infinite
amount of solvent B. The enthalpy of combining these two substances to form the solution is ΔH3 and is an exothermic
reaction (releasing heat since interactions are formed) with ΔH3<0.
A(g)+B(g)→A(sol) (energy out)
So the enthalpy of solution can either be endothermic, exothermic or neither (ΔHsolution=0), depending on how much heat
is required or released in each step. If ΔHsolution = 0, then the solutions are called ideal solutions and if ΔHsolution>0 or
ΔHsolution<0, then these solutions are called non-ideal solutions.

The two most important state sizes to describe the energy/ heat content change of a substance are the inner energy and
the enthalpy. The shortest form to describe change of inner energy is given in the so called first sentence of
Thermodynamics.

dU = δQ + δW

Where δQ is the heat and δW the work change of the regarded system. In the following, many different ways of heat
production are considered but for the work change is taken care of volume work. The enthalpy is in some ways more
convenient and easier to control state size than the inner energy, where changes are described through

dH = dQ + d(pV) = δQ + Vdp

Both inner energy and enthalpy are only defined in so called closed systems (exchange of energy and/ or heat, no
exchange of matter). Formula (1) and (2) can be simplified if pressure or volume are constant
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

dU = δQ (for V = const.)

dH = δQ (for p = const.)

At constant pressure as regarded in 4.), enthalpy changes are directly proportional to the heat added and to a specific
size Cp of a system, where Cp is the heat capacity [J mol−1 K−1] by constant pressure of the given substance. This
correlation can be described through

∆H = ∆Q = Cp∆T

One can find the characteristic size Cp of substances listed at tables in the literature. Therefore, through knowing Cp and
temperature change of a chemical transformation by constant pressure, the heat loss or gain of the transformation can be
calculated and therefore directly ∆H too.

Calculations:

Determining: Water equivalent K

Heat Capacity of pure components Q = IV t

IVt = mCpΔT + αΔT

Q = mCpΔT + αΔT

Heat of mixing for different mixture compositions Qm = (mCpm + α)(−ΔTm)

Partial molar enthalpies at different compositions and infinite dilution

dΔhmix
̅1 − h1 = Δhmix − x2 ∗ (
h )
𝑑𝑋2
dΔhmix
̅ 2 − h2 = Δhmix − x1 ∗ (
h )
𝑑𝑋1

Experiment Details

Materials Required

1. Chemicals:
 Iso Propyl Alcohol
 Distilled Water

2. Instruments:
 Weighing Balance: Useful when determining required weights for water Iso Propyl Alcohol mixtures.
Least Count: 0.001g
 Beaker(250,150ml): Used to store water and Iso Propyl Alcohol
 Magnetic Stirrer: Ensures uniform heat transfer and temperature throughout the mixture
 Adiabatic Flask: Holds the water Iso Propyl Alcohol mixture and ensure minimal heat leakage to
surroundings
 Electric Heater: Heats the mixture inside the adiabatic flask. P=250W
 Thermocouple: Measures the temperature of the mixture. Least Count: 0.1K
 Measuring Flask

Setup & Procedure

Calibration
 Make sure all the apparatuses are clean and ready to use
 First place the Adiabatic Flask over the magnetic stirrer
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

 Pour 100 gms of water into the flask using the measuring flask
 Now close the lid of the flask and insert both the electric heater and thermocouple into the flask through the holes
in the lid
 Measure the steady state temperature of water
 Now switch on the 250W heater for 10 seconds
 Note down the steady state temperature after the heating
 As a result, α (flask constant) can be calculated by using the equation described below

Experiment
 Now as per our objective we mix Iso Propyl Alcohol and water with Iso Propyl Alcohol mole fraction equal to
0.2,0.4,0.5,0.6,0.8 in different cases and put it inside the flask.
 Record the steady state temperature of the mixture
 Now heat the mixture with the 250W heater for 10 seconds and record the steady state temperature
 Now calculate Cpmix from the equation given below
 Using the Cpmix and alpha value calculated from calibration find Qmix
 This Qmix divided by total no. of moles will give hmix
 Repeat these steps for the cases and calculate hmix for each case

Experimental Observations and Data with Calculations

Calculation of Loss Coefficient α

Q = (Cp * m + α )* ΔT

Sample Calculation:

Q = 2500 J ; Cp = 4.18 Jg-1K-1 ; ΔT = ; m = 100 g;

2500 = (4.18 * 100 + α )* 3.4

The above equation gives α = 317.2941 JK-1

Calculation of Cp of Mixture by heating by measuring the Temperature Change

Q = (Cp,mix * m + α )* ΔT

Sample Calculation:

Q = 2500 J ; ΔT = ; m = 100 g; α=

2500 = (Cp,mix * 100 + 340.2721 )* 3.6

The above equation gives Cp,mix = 3.5417 Jg-1K-1
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

Calculation of Enthalpy of Mixing

Qmix = (Cp,mix * m + α )* ΔTmix

Δhmix = -Qmix/ntotal

Sample Calculation:

Cp,mix = 5.5258 Jg-1K-1 ; ΔTmix = 6.5 K; m = 100 g; α = 340.2721 JK-1; ntotal = 4.2373 moles;

Qmix = (5.5258 * 100 + 340.2721 )* 6.5

The above equation gives Qmix = 5803.5714 J

Δhmix = -5803.5714/4.2373

The above equation gives Δhmix = -1369.6428 Jmol-1

Plot of Enthalpy of Mixing vs Mole Fraction of Iso Propyl Alcohol

Plot of Enthalpy of Mixing vs Mole Fraction of Iso Propyl Alcohol

Calculation of Partial Molar Enthalpy

MATLAB Code
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

Calculation of Relative Partial Molar Enthalpy

ħ1 = ̅̅̅
h1 − h1
ħ2 = ̅̅̅
h2 − h2

∆𝐡𝐦𝐢𝐱 = −𝐱 𝟏 . 𝐱 𝟐 . (𝟐𝟔. 𝟏𝟐𝟖𝟑𝐱 𝟏𝟐 − 𝟑𝟕. 𝟗𝟎𝟕𝟕𝐱 𝟏 + 𝟏𝟒. 𝟗𝟐𝟑𝟑)𝐊𝐉

Result
 The heat loss coefficient of the flask was calculated to be 340.2721 JK -1.
 The Cp,mix was calculated for various compositions by supplying a known amount of heat and measuring
temperature change.
 The Cp calculated decreases with increase in mole fraction of Iso Propyl Alcohol . It is initially close to Cp,water and
approaches Cp,Iso Propyl Alcohol .
 The ∆hmix was calculated for varying ratios of mixing and was plotted against mole fraction of water and Iso
Propyl Alcohol .
 The ∆hmix is negative implying an Exothermic Reaction.

 Comparison of ∆hmix from experiment with the values from literature show significant deviations.
 ∆hmix decreases in magnitude as we increase X1 and increases in in magnitude with increase in X2
∆hmix
 was plotted against x1 and a quadratic fit was developed which yielded the equation
x1 x2
∆𝐡𝐦𝐢𝐱 = −𝐱 𝟏 . 𝐱 𝟐 . (𝟐𝟔. 𝟏𝟐𝟖𝟑𝐱 𝟏𝟐 − 𝟑𝟕. 𝟗𝟎𝟕𝟕𝐱 𝟏 + 𝟏𝟒. 𝟗𝟐𝟑𝟑)𝐊𝐉
 The quadratic fit was plotted alongside the experimental data and was found to explain the trend in data
sufficiently.
 We get a 4th order expression for ∆hmix in mole fraction of Iso Propyl Alcohol or water.
 By plotting the ∆hmix vs X1 and ∆hmix vs X2 and using the slope intercept formula, the relative partial molar
enthalpies at different mole fractions was calculated.
 For small mole fractions, the relative molar enthalpy becomes very small and thus the partial molar enthalpy
becomes close to molar enthalpy of the pure species.
 For large mole fractions, the relative molar enthalpy increases and the partial molar enthalpy approaches the
infinite dilution partial molar enthalpy.

Discussions
 The flask is not an ideal adiabatic wall, Therefore the coefficient of heat loss had to be calculated.
 To simplify the experiment, α was taken to be a constant property of the flask independent of the liquid used,
temperature and time.
 Theoretically the Cp,mix should follow the equation
Cp,mix = x1 ∗ Cp1 + x2 ∗ Cp2
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

 But we find Cp,mix to be greater than Cp1 and Cp2. This may be because of the wrong assumption that α doesn’t
change with T and liquid used.
 Cp,mix however approaches Cp1 when X1 is large and vice-versa implying that the species precent in higher
concentration contributes more to the heat capacity as predicted by the linear relation.
 Iso Propyl Alcohol and water do not form an ideal mixture. Therefore . ∆ℎ𝑚𝑖𝑥 ≠ 0
 The ∆ℎ𝑚𝑖𝑥 was negative implying a positive deviation from Raoult’s law as heat is evolved by mixing.
 The A-B bonds between H2O and Iso Propyl Alcohol are stronger than the A-A and B-B interactions.
 This is because of H-Bonding between Iso Propyl Alcohol and Water which form more stable bonds and thus
releases more energy than is required to break A-A and B-B bonds.
 As number of Iso Propyl Alcohol molecules increases, they compete with the limited water molecules and thus
due to steric effects, the H-Bonding becomes less efficient. So with increase in X1, the∆ℎ𝑚𝑖𝑥 becomes smaller in
magnitude.
 However, as the mole fraction of water is increased, the H-Bonding becomes more prominent and thus increases
the heat evolved on mixing.
∆ℎ𝑚𝑖𝑥
 The plot of showed polynomial trends and was thus fitted with a quadratic equation. A cubic equation,
𝑥1 𝑥2
improves the fit only by a marginal amount.
 Since, there are only 5 data points the fit is cannot be generalised.
∆ℎ𝑚𝑖𝑥
 The determinant for is negative and the coefficient of x2 is also negative. This shows that the enthalpy of
𝑥1 𝑥2
mixing is negative irrespective of the concentration.
 At mole fractions tending to unity for a species, the entire contribution to the enthalpy of mixture is from that
species. This is seen as the relative partial molar enthalpy approaches 0 and the partial molar enthalpy value
tends close to the pure species molar enthalpy.
 Comparing ∆ℎ𝑚𝑖𝑥 with literature gives a significant deviation because of the underlying assumptions made -
o Both liquids are at the same temperature prior to mixing
o 𝛼 is a constant of the flask.
o Cp is constant in the given temperature range.
o Heat Loss in flask is linearly dependant on Temperature.
 However, the model is useful to show the decreasing trend on negative enthalpy of mixing.

Conclusion
 Iso Propyl Alcohol and water form a non-idea mixture and exhibit positive deviation from Raoult’s Law at all
concentrations.
 The Enthalpy of mixing is negative and decreases with increase in Iso Propyl Alcohol concentration in the given
range of concentrations.
∆ℎ𝑚𝑖𝑥
 By regression for vs X1 a good fit can be obtained for ∆ℎ𝑚𝑖𝑥 which is 4th order in mole fraction.
𝑥1 𝑥2
 The ∆ℎ𝑚𝑖𝑥 was plotted and using tangent-intercept method, relative partial molar enthalpies were obtained at
various concentrations.

References:
M. D. Koretsky, Engineering and Chemical Thermodynamics; 2nd Edition, Wiley: New York, 2012; pp 263-287.