YILDIZ TECHNICAL UNIVERSITY

FACULTY OF SCIENCE & ART

DEPARTMENT OF CHEMISTRY

2020-2021 FALL

PHYSICAL CHEMISTRY 1

Lecture Notes

THERMOCHEMISTRY

Lecturer: Prof. Dr. Nergis ARSU

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 THERMOCHEMISTRY

(Application of the first law of thermodynamics to chemical reactions - The heat of

rection)

Thermochemistry is the branch of thermodynamics that investigates the heat flow into or out

of a reaction system and deduces the energy stored in chemical bonds. As reactants are

converted into products, energy can either be taken up by the system or released to the

surroundings. For a reaction that takes place at constant volume, the heat that flows to or out

of the system is equal to ΔU for the reaction. For a reaction that takes place at constant

pressure, the heat that flows to or out of the system is equal to ΔH for the reaction.

- If the system is hotter after the reaction than before heat must flow to the surroundings

to restore the system to the initial temperature. In this event the reaction is exothermic and the

heat of reaction(ΔH) is negative.

- If the system is colder after the reaction than before heat must flow from the

surroundings to restore the system to the initial temperature. In this case reaction is

endothermic and the heat of reaction(ΔH) is positive.

The enthalpy of formation is defined as the heat flow into or out of the system in a reaction

between pure elements that leads to the formation of 1 mol of product. Because H is a state

function, the reaction enthalpy can be written as the enthalpies of formation of the products

minus those of the reactants. This property allows ΔU and ΔH for a reaction to be calculated

for many reactions without carrying out an experiment.

In the laboratory the majority of chemical reactions are performed under a constant pressure;

therefore, the heat withdrawn from the surroundings is equal to the change in enthalpy of the

system. To avoid mixing the enthalpy change associated with the chemical reaction and that

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associated with a temperature or pressure change in the system, the initial and final states of

the system must have the same temperature and pressure.

For example, in the reaction;

At a specified temperature and pressure, the molar H of each substance has a definite value.

The Formation Reactions

The formation reaction of a compound has one mole of the compound and nothing else on the

product side, only elements in their stable states of aggregation appear on the reactant side.

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The increase in enthalpy in such a reaction is the heat of formation, or enthalpy of formation,

of the compound, ΔHf. The following reactions are examples of formation reactions;

H2(g) + ½ O2(g)  H2O(l)

2Fe(s) + 3/2 O2(g)  Fe2O3(s)

If the ΔH for these reactions is written in terms of the molar enthalpies of the substances,

we obtain, using the first two as examples,

ΔHf(H2O, l) = H(H2O, l) – H(H2, g) – ½ H(O2, g)

ΔHf (Fe2O3, s) = H(Fe2O3, s) – 2H(Fe, s) – 3/2 H(O2, g)

Solving for the molar enthalpy of the compound in each example, we have;

H(H2O, l) = H(H2, g) + ½ H(O2, g) + ΔHf(H2O, l)

H(Fe2O3, s) = 2H(Fe, s) + 3/2 H(O2, g) + ΔHf (Fe2O3, s)

These equations show that the molar enthalpy of a compound is equal to the total enthalpy

of the elements that compose the compound plus the enthalpy of formation of the compound.

Thus, we can write for any compound,

H(compound) = ΣH(element) + ΔHf(compound)

The enthalpy of formation (ΔHf) of a compound at 1 atm pressure is the standard enthalpy of

formation(ΔHof).

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The Determination of Heats of Formation

In some cases, it is possible to determine the heat of formation of a compound directly by

carrying out the formation reaction in a calorimeter and measuring the heat effect produced.

The majority of formation reactions are unsuitable for calorimetric measurements, these heats

of formation must be determined by indirect methods. For example,

There is one method that is generally applicable if the compound burns easily to form definite

products. The heat of formation of a compound can be calculated from the measured value of

the heat of combustion of the compound.

The combustion reaction has one mole of substance to be burned on the reactant side, with as

much oxygen as is necessary to burn the substance completely, organic compounds containing

only carbon, hydrogen and oxygen are burned to gaseous carbon dioxide and liquid water.

In terms of the enthalpies of the individual substances.

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The measurement of the heat of combustion is used to determine the heats of formation of all

organic compounds that contain only carbon, hydrogen and oxygen. These compounds burn

completely to CO2 and H2O in calorimeter.

Sequences of Reactions: Hess Law

The change in state of a system produced by a specified chemical reaction is definite. The

corresponding enthalpy change is definite, since the enthalpy is a function of the state.

If we transform a specified set of reactants to a specified set of products by more than one

sequence of reactions, the total enthalpy change must be the same for every sequence.

This rule, which is consequence of the first law of thermodynamics, was originally known as

Hess’ law of constant summation.

We compare two different methods of synthesizing NaCl from Na and Cl.

Method 1

Method 2

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The net chemical change is obtained by adding together all the reactions in the sequence; the

net enthalpy change is obtained by adding together all the enthalpy changes in the sequence.

The net enthalpy change must be the same for every sequence which has the same net

chemical change. Any number of reactions can be added or subtracted to yield the desired

chemical reaction; the enthalpy changes of the reactions are added or subtracted algebraically

in the corresponding way.

Question:

Calculate the heat of formation of CH4 according to the below equation.

Heats of Solution and Dilution

The heat of solution is the enthalpy change associated with the addition of a specified amount

of solute to a specified amount of solvent at constant temperature and pressure. For

convenience we shall use water as the solvent in the illustrations, but the argument can be

applied to any solvent with slight modification. The change in state is represented by
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One mole of solute X is added to n moles of water. The water is given the symbol Aq in this

equation; it is convenient to assign a conventional enthalpy of zero to the water in these

solution reactions.

Question:

The values of H show the general dependence of the heat of solution on the amount of

solvent. As more and more solvent is used, the heat of solution approaches a limiting value,

the value in the “infinitely dilute” solution. For HCl this limiting value is given by H5.

The Heat of Formation of Solution

Determination of Enthalpy of Reaction from Bond Energies

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When a chemical bond breaks, heat needs to given from surrounding to system H > 0

When a chemical bond forms, system is more stable and gives heat to surroundings H < 0

If we consider the atomization o f a gaseous diatomic molecule,

O2(g)  2 O(g) ΔHo298 = 498.34 kJ/mol

the value 498.34 kJ is called the bond enthalpy of the oxygen molecule.

H2O(g)  2H(g) + O(g) ΔHo298 = 926.98 kJ/mol

1/2(926.98) = 463.49 kJ/mole the average bond enthalpy of the O-H bond in water.

Question: The complete combustion of propane. Calculate ΔH.

CH3CH2CH3(g) + 5O2(g)  3CO2(g) + 4H2O(g)

Bond Energy kJ/mol

C-H 413

C-C 347

O=O 498

C=O 805

O-H 464

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Breaks Forms

2 x C-C 6 x C=O

8 x C-H 8 x O-H

5 x O=O

=6488 kJ/mol =8542 kJ/mol

ΔH = 6488 – 8542 = -2054 kJ/mol

Heats of Reaction at Constant Volume

If any of the reactants or products of the calorimetric reaction are gaseous, it is necessary to

conduct the reaction in a sealed bomb. Under this condition the system is initially and finally

in a constant volume rather than being under a constant pressure.

The measured heat of reaction at constant volume is equal to an energy increment, rather than

to an enthalpy increment:

V = constant Reactants(T, V, P1) Products(T, V, P2)

ΔH = ΔH2 – ΔH1

ΔH = (U2 + P2V2) – (U1 + P1V1) V 1 = V2

ΔH = (U2-U1) + V(P2-P1)

ΔH = ΔU + ΔP

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Qp = Qv + VΔP

If gases are ideal;

Qp = Qv + V

Qp = Qv + (nP – nR)RT

Qp = Qv + ΔnRT

ΔH = ΔU + ΔnRT

Dependence of the Heat of Reaction on Temperature – Kirchoff’s Equations

P = constant Ho = Hoproducts - Horeactants

To find dependence of this quantity on temperature, we differentiate with respect to

temperature.

Question: Calculate the Ho at 85oC for the reaction

Fe2O3(s) + 3 H2(g)  2 Fe(s) + 3 H2O(l) Ho298 = -33.29 kJ/mol

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 Substance Fe2O3(s) Fe(s) H2O(l) H2

Cpo (J/mol K) 103.8 25.1 75.3 28.8

Cpo = [(2 x Cpo(Fe,s)) + (3 x Cpo(H2O,l))] – [Cpo(Fe2O3,s) + (3 x Cpo(H2,g))]

Cpo = [(2 x 25.1) + (3 x 75.3)] – [103.8 + (3 x 28.8)]

Cpo = 85.9 J/mol K

T = 85 + 273 = 358 K

358

Ho358 = Ho298 + ∫ 85.9 dT =−28.14 kJ /mol

Adiabatic Flame Temperature

In the absence of any work interactions and any changes in kinetic or potential energies, the

chemical energy released during a combustion process either is lost as heat to the

surroundings or is used internally to raise the temperature of the combustion products.

The smaller the heat loss, the larger the temperature rise. In the limiting case of no heat loss to

the surroundings (Q = 0), the temperature of the products reaches a maximum is called the

adiabatic flame or adiabatic combustion temperature of the reaction.

The temperature of a combustion chamber becomes maximum when combustion is complete,

and no heat is lost to the surroundings (Q = 0).

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Tf : Adiabatic flame temperature

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