11.

Thermochemistry

11.1 Thermodynamics

11.1.1 Define thermodynamics [K]

In thermodynamics we study the energy changes that accompany physical and

chemical processes. These energy changes usually involve heat—hence the “thermo-”
part of the term.

11.1.2 Define the terms, system, surrounding, state function, heat,

internal energy, work and enthalpy [K]

01. System & Surrounding

The substances involved in the chemical and physical changes that we are studying are
called the system. Everything in the system’s environment constitutes its surroundings.

The First Law of Thermodynamics tells us that energy is neither created nor destroyed;
it is only transferred between the system and its surroundings.

Boundary: any real or imaginary line that separates the system from surrounding

02. State Function

A state function is a macroscopic property of a system which has some

definite values for initial and final states, and which is independent of the
path adopted to bring about a change OR

The properties of a system (such as P, V, T) are called state functions.

The value of a state function depends only on the state of the system and not on the
way in which the system came to be in that state.

For instance, consider a sample of one mole of pure liquid water at 30°C and 1 atm
pressure. If at some later time the temperature of the sample is 22°C at the same
pressure, then it is in a different thermodynamic state. We can tell that the net
temperature change is 8°C. It does not matter how the temperature is achieved.

The most important use of state functions in thermodynamics is to describe changes.

We describe the difference in any quantity, X, as:
03. Heat & Work: Two forms of energy transfer

Heat

It is defined as the quantity of energy that flows across the boundary of a system
during a change in its state due to the difference in temperature between the system
and the surroundings

Heat or thermal energy (symbolized by q) is the energy transferred as a result of a

difference in temperature between the system and the surroundings. For example,
energy in the form of heat is transferred from hot soup (system) to the bowl, air, and
table (surroundings) because they are at a lower temperature.

Work

It is defined as the product of force and distance i.e. W = F x S.

Work is measured in Joules in SI units.

Work is the transfer of energy by any process other than heat.

Like heat, the unit measurement for work is joules (J).

04. Internal Energy

All forms of energy associated with a specific amount of a substance. OR

Each particle in a system has potential energy and kinetic energy, and the sum of all
these energies is the internal energy, E, of the system (some texts use the symbol U).
When the reactants in a chemical system change to products, the system’s internal
energy has changed.
E is a transfer of energy from system to surroundings, or vice versa.

05. Enthalpy: changes at constant pressure

Most chemical reactions and physical changes occur at constant (usually atmospheric)
pressure.

An enthalpy change is sometimes loosely referred to as a heat change or a heat of

reaction. It is impossible to know the absolute enthalpy (heat content) of a system.
Enthalpy is a state function, however, and it is the change in enthalpy in which we are
interested; this can be measured for many processes.
∆H= ∆E +P∆V
11.2 First Law of Thermodynamics

11.2.1 State and explain the first law of thermodynamics with the help
of daily life examples [U]

The total amount of energy in the universe is constant (also known as the Law of
Conservation of Energy); energy is neither created nor destroyed in ordinary chemical
reactions and physical changes. OR

The First Law of Thermodynamics states that energy can be converted from one form
to another with the interaction of heat, work and internal energy, but it cannot be
created nor destroyed, under any circumstances. Mathematically, this is represented as
∆E = E -E
∆E = q+w

In this text we always take the system’s point of view.

Daily life applications will be discussed at the end of chapter.

11.2.2 Relate change in internal energy of system with thermal energy

at constant volume and pressure [U]

Derivation of w = P. ∆V

Suppose we have a gas confined to a cylindrical container with a movable piston

as shown in Figure, where F is the force acting on a piston of area A. Since
pressure is defined as force per unit area, the pressure of the gas is
Work is defined as force applied over a distance, so if the piston moves a distance h, as
shown in Figure, then the work done is

Since the volume of a cylinder equals the area of the piston times the height of
the cylinder (see Figure), the change in volume ∆V resulting from the piston
moving a distance ∆h is

The gas (the system) is expanding, moving the piston against the pressure. Thus the
system is doing work on the surroundings, so from the system’s point of view the sign
of the work should be negative.
For an expanding gas, ∆V is a positive quantity because the volume is increasing. Thus

∆V and W must have opposite signs, which leads to the equation.

Note that for a gas expanding against an external pressure P, w is a negative quantity
as required, since work flows out of the system. When a gas is compressed, ∆V is a
negative quantity (the volume decreases), which makes w a positive quantity (work
flows into the system).

Change in Internal energy at constant Volume and constant pressure

We know from first law of thermodynamics.

∆E = q + w
At constant pressure
∆E = qp - P∆V OR qp = ∆E + P∆V
Heat of the reaction at constant pressure is called enthalpy, H and we can write enthalpy
change as

qp = ∆H = ∆E + P∆V
∆E = ∆H - P∆V

At constant Volume, w = 0
qv = ∆E + P∆V
∆E= qv
Heat of the reaction at constant volume is ∆E or ∆U

Practice Problem

Calculate internal energy change for the following reaction.

Solution
From Gas law we can write P∆V = ∆n RT
11.2.3 Calculate internal energy and work done of a system by
applying the first law of thermodynamics [A]

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Always include the sign of ΔU (and of ΔX in general), even if it is positive.
11.3 Hess’s Law

11.3.1State and explain Hess’s law of heat summation [U]

Enthalpy is a state function. Its change is therefore independent of the pathway by

which a reaction occurs. We do not need to know whether the reaction does, or even
can, occur by the series of steps used in the calculation. The steps must (if only “on
paper”) result in the overall reaction.

Here a, b, c, . . . refer to balanced thermochemical equations that can be summed to

give the equation for the desired reaction.

Standard enthalpies of individual reactions can be combined to obtain the enthalpy of

another reaction

11.3.2 Construct simple energy cycles by using Hess’s law for any
given reactions [A]

Consider the following reaction.

The enthalpy change for this reaction cannot be measured directly. But following
reactions do go to completion.

We can manipulate the above equations to get the enthalpy change of the desired
reaction.
A simple energy cycle is given below.

11.3.3 Calculate standard heat of formation and heat of reaction by

using Hess’s law [A]

The term standard state refers to the standard thermodynamic conditions chosen for
substances when listing or comparing thermodynamic data: 1 atm pressure and the
specified temperature (usually 25oC).

The enthalpy change for a reaction in which reactants in their standard states
yield products in their standard states is denoted Ho (“delta H degree,” but often
read as “delta H zero”). The quantity Ho is called the standard enthalpy of reaction.

The International Union of Pure and Applied Chemists (IUPAC) has adopted 1 bar
(100,000 Pa) as the standard pressure instead of 1 atm (101,305 Pa). Both standards are
now in wide use.

Standard state is not the same as the standard temperature and pressure (STP) for a
gas.
Enthalpies of formation are always given per mole of product with the product in its
standard state. The formation reaction for methanol is written as

Methanol is represented as one mole in equation. not as 2C, 4H2, O2, and 2CH3OH

Standard heat of formation or enthalpy of formation

The standard enthalpy of formation (also called the standard heat of formation) of
a substance, denoted Ho is the enthalpy change for the formation of one mole of
the substance in its standard state from its elements in their standard states.

Consider the standard enthalpy of formation of liquid water.

The stablest forms of hydrogen and oxygen at 1 atm and 25oC are H2(g) and O2(g),
respectively.

ELEMENT

The standard enthalpy of formation of an element will depend on the form of the
element.
We can use standard enthalpies of formation to find the standard enthalpy change for a
reaction. Consider the following reaction.

And you have this data

So you can also calculate heat of the reaction in the following manner.

The key point is if you are given heat of formation of individual components you
can calculate heat of the reaction.

Enthalpies of formation can also be defined for ions. It is not possible to make thermal
measurements on individual ions, so we must arbitrarily define the standard enthalpy of
formation of one ion as zero. The standard enthalpy of formation of H+ (aq) is taken as
zero.

A special case of Hess’s Law

The net enthalpy change of a reaction is the amount of energy required to break all the
bonds in reactant molecules minus the amount of energy required to break all the
bonds in product molecules.

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Now also calculate the heat of the reaction form heat of the formation data from table.
H = product - reactant
H = [-277.7] - [(-285.8) + (52.47)]
H = -277.7 - (-233.33)
H = -277.7 + 233.33
H = - 44.37 kJ/mol rxn
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11.3.4 Explain working of a calorimeter (glass and bomb calorimeter) [U]

We can determine the energy change associated with a chemical or physical process by
using an experimental technique called calorimetry. Calorimeter is a device used to
measure the heat absorbed or evolved during a physical or chemical change. For
reactions involving gases, a bomb calorimeter is generally used. In bomb calorimeter
reactions are done under constant volume conditions so it will give the value of U or
E. For reactions involving no gases we can use a “coffee-cup” calorimeter. This
calorimeter operates under constant pressure conditions and it gives the value of H.

Working

In a calorimeter, we measure the rise in the temperature of the solution that is

surrounding the reaction vessel. For an exothermic reaction, the amount of heat
evolved by the reaction can be calculated from the amount by which it causes the
temperature of the calorimeter and the solution to rise.

The quantity of energy released can be calculated from the temperature increase, the
mass of solution, and the specific heat capacity of the solution.
In a bomb calorimeter as shown in diagram the reaction is carried out inside a rigid
steel “bomb”, and the heat evolved is absorbed by the surrounding water and other
calorimeter parts. The quantity of energy produced by the reaction can be calculated
from the temperature increase. For any exothermic reaction.

If we know the mass of the sample and the heat capacity of the entire calorimeter, we
can use the measured T to calculate the heat released. In a bomb calorimeter w = 0,
so the heat released at constant volume (qV), is equals E and not H:

The glass bomb calorimeter

The results produced from the steel bomb are not reproducible to a high enough
degree of accuracy. The steel calorimeter has a problem in that the results obtained
vary by up to 15% from one run to another. The upshot of this is that the calorimeter
only really gives an indication rather than an absolute value. The glass bomb gives
reproducable results which vary with a maximum of 1%.

Glass bomb calorimeter advantages are given below.

a) The experiments are far more convenient. This is because to the bomb does not
require a circulating water bath. Also smaller amounts of sample are used (between
0.3 g and 0.7 g are all that are typically required for a result compared to around 1g
for the conventional steel bomb calorimeter).

b) The experiment is far more accurate.

c) The experiment is more reproducable.

11.3.5 Calculate the heat of reaction in a calorimeter from the given

experimental data [A]

FOR A “COFFEE-CUP” CALORIMETER

If a hot solid body is immersed in the water and the temperature increase is monitored
then
AN AQUEOUS ACID-BASE REACTION

Recall that, if a reaction takes place at constant pressure, the heat of the reaction (qrxn) is
equal to its enthalpy change (H).

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Practice Problem : Bomb Calorimeter
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11.4 Born-Haber Cycle

The lattice energy is the change in energy that occurs when an ionic solid is separated
into isolated ions in the gas phase.

11.4.1 Explain reaction pathway diagram in terms of enthalpy

changes of the reactions (of ionic compounds) using Born-Haber’s
cycle [U]

Direct experimental determination of the lattice energy of an ionic solid is difficult.

However, this quantity can be indirectly determined from experiment by means of a
thermochemical “cycle” called the Born–Haber cycle.

To obtain the lattice energy of NaCl. There are two possibilities

In one route, NaCl(s) is formed directly from the elements, Na(s) and 1/2 Cl2(g). The
enthalpy change for this is Hof, which is 411 kJ per mole of NaCl. The second route
consists of five steps.
The enthalpy of formation has been determined calorimetrically and equals 411 kJ.
Equating these two values, we get
11.4.2 Calculate lattice energy and enthalpy of formation of ionic
compounds from given set of appropriate data [A]

Practice Problem
11.5 Heat Capacity

11.5.1 Describe the terms, heat capacity, specific heat capacity and
molar heat capacity [U]

Heat Capacity: The amount of energy require to raise the temperature of any
substance by one degree Celsius.

Specific heat capacity: the energy required to raise the temperature of one gram of a
substance by one degree Celsius.

If we know c of the object being heated (or cooled), we can measure the mass and the
temperature change and calculate the heat absorbed (or released):

Molar heat capacity: the energy required to raise the temperature of one mole of a
substance by one degree Celsius.
Practice Problem

Real Life Applications

1. When we add an ice cube in the lemonade. You will notice that the ice has melted
but the temperature of the lemonade has cooled. This is because the total amount of
heat in the system has remained the same, but has just gravitated towards equilibrium,
where both the former ice cube (now water) and the lemonade are the same
temperature.

2. If many people are in a closed room. Heat from your body is transferred to the
sweat. As the sweat absorbs more and more heat, it evaporates from your body,
becoming more disordered and transferring heat to the air, which heats up the air
temperature of
the room. Many sweating people in a crowded room, "closed system," will quickly heat
things up. No heat is lost; it is merely transferred from human body to environment.

3. If you are in a warm water tub. The water feels comfortably warm, because the
water's temperature is higher than the person's body temperature. After some time,
however, some heat from the water will have transferred to the individual, and the
two temperatures will meet. After a bit more time has passed, because this is not a
closed system, the bath water will cool as heat is lost to the atmosphere.

4. Even cooling machines, such as refrigerators and air conditioners, actually use
heat, simply reversing the usual process by which particles are heated. The
refrigerator pulls heat from its inner compartment—the area where food and other
perishables are stored—and transfers it to the region outside. This is why the back of
a refrigerator is warm.
You do not need to remember this table. All the required values will be given in
examination.