LECTURE 6 – HEAT TRANSACTIONS

6.1. HEAT TRANSACTIONS

It is energy that spontaneously passes between a system and its surroundings in some way other
than through work or the transfer of matter. When a suitable physical pathway exists, heat flows
spontaneously from a hotter to a colder body.
First Law of Thermodynamics:
∆𝑈 = Q + W
Internal energy can be written as:
dU = dQ + dW exp + dW e
dQ heat: energy transferred across boundary due to difference in T
dW exp work due to expansion
dWe extra sources of work (e.g., electrical current)
• At constant V, dW exp = 0 (system cannot expand)
• If no additional work (no battery, etc.), dWe = 0
dU = dQ
Write dU = dqv, which implies infinitesimal change at constant volume. Thus for a measurable finite
change:
ΔU = Qv
Note: q > 0 (heat supplied to system)
q < 0 (heat lost from system)

(a.) CALORIMETRY
Calorimetry is the process of measuring the amount of heat
released or absorbed during a chemical reaction. By knowing the
change in heat, it can be determined whether or not a reaction is
exothermic (releases heat) or endothermic (absorbs heat).
Calorimetry also plays a large part of everyday life, controlling the
metabolic rates in humans and consequently maintaining such
functions like body temperature.
How do we study changes in energy due to addition or
subtraction of heat in a system? We can use an adiabatic bomb
calorimeter
Adiabatic: Implies that the device is isolated from the outside world,
such that no thermal transfer of energy can take

RVM Lecture Manual: Physical Chemistry 1 1

 place between system and surroundings
Bomb: The sturdy vessel with constant volume inside which very vigorous reactions, combustions and
explosions can take place at high pressure
Calorimeter: From the cgs unit of energy, the calorie, implying the measurement of energy

How does a bomb calorimeter work?

1. Reaction is conducted in the constant volume bomb.
2. Bomb is immersed in a stirred water bath, forming the
calorimeter
3. Calorimeter is immersed in a second water bath, the
temperature of which is continuously adjusted to the
temperature of the bomb bath, thereby ensuring an adiabatic
system

A chemical reaction either releases or absorbs heat, causing a

proportional change in temperature ΔT of the calorimeter:
Measuring ΔT allows us to determine qV, and therefore ΔU -
BUT.... we must calibrate the calorimeter using known energy to get the
calorimeter constant, C
Q = CΔT

(a.1.) CONSTANT PRESSURE CALORIMETRY

Because calorimetry is used to measure the heat of a reaction, it is a crucial part of thermodynamics.
In order to measure the heat of reaction, the reaction must be isolated so that no heat is lost to the
environment. This is achieved by use of a calorimeter, which insulates the reaction to better contain heat.
Coffee cups are often used as a quick and easy to make calorimeter for constant pressure. More sophisticated
bomb calorimeters are built for use at constant volumes.
Using calorimetry, it is possible to calculate the amount of heat gained and lost by each part of the
system. The amount of heat lost or gained by any part of the reaction is related to the heat capacity of the
substance. Heat capacity is the amount of energy, Q, needed to raise the temperature 1℃ or 1 K. To calculate
the amount of heat released or absorbed by a reaction in terms of ∆𝑇, the equation for object’s total heat
capacity (below is used:
𝑄 = 𝐶 𝑥 ∆𝑇
Where
• Q is the amount of heat gained or lost
• C is the object’s total heat capacity
• ∆𝑇 is final temperature – initial temperature
The total heat capacity of an object (or sample) can be decomposed into one or two subsequent
relationships. Either based on mass:
𝐶 = 𝑚 𝑥 𝐶𝑠𝑝
Or based on the number of atoms or molecule in the object:
𝐶 = 𝑛 𝑥 𝐶𝑝
Where:
• M is the mass of the object in units of g
• Csp is the specific heat of the object in units of 𝐽/𝑔℃
• n is the number of mole of molecules in the object in units of mole
• Cp is the molar heat capacity in units of 𝐽/𝑔℃ (specifically nder constant pressure; it would
be Cv under constant volume
Specific heat capacity takes into account the mass of a substance and the energy needed to raise its
temperature by ∆𝑇, as shown by combining equations:
𝑄 = 𝑚 𝑥 𝐶𝑠𝑝 𝑥 ∆𝑇

RVM Lecture Manual: Physical Chemistry 1 2

 Theoretically, the qproducts should be equivalent to qreactants because the amount of heat gained by one
substance should be equal to the amount lost by another. However, the calorimeter also absorbs some of the
heat form the reaction. Because of this, the heat capacity of the calorimeter is also necessary for calculations
and results in the following equation:
𝑞𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 + 𝑞𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 + 𝑞𝑐𝑎𝑙𝑜𝑟𝑖𝑚𝑒𝑡𝑒𝑟 = 0

(a.2) Constant Volume Calorimetry

Constant Volume Calorimetry, also known as bomb calorimetry, is used to measure the heat of a
reaction while holding volume constant and resisting large amounts of pressure. Although these two aspects
of bomb calorimetry make for accurate results, they also contribute to the difficulty of bomb calorimetry.
Calorimetry is used to measure quantities of heat, and can be used to determine the heat of reaction
through experiments. Usually a coffee-cup calorimeter is used since it is simpler than a bomb calorimeter, but
to measure the heat evolved in a combustion reaction, constant volume or bomb calorimetry is ideal.
Most serious calorimetry carried out in research laboratories involves the determination of heats of
combustion, since these are essential to the determination of standard enthalpies of formation of the
thousands of new compounds that are prepared and characterized each month. In a constant volume
calorimeter, the system is sealed or isolated from its surroundings, and this accounts for why its volume is
fixed and there is no volume-pressure work done. A bomb calorimeter structure consists of the following:
• Steel bomb which contains the reactants
• Water bath in which the bomb is submerged
• Thermometer
• A motorized stirrer
• Wire for ignition
Since the process takes place at constant volume, the reaction vessel must be constructed to
withstand the high pressure resulting from the combustion process, which amounts to a confined explosion.
The vessel is usually called a “bomb”, and the technique is known as bomb calorimetry. The reaction is
initiated by discharging a capacitor through a thin wire which ignites the mixture.
Another consequence of the constant-volume condition is that the heat released corresponds to qv,
and thus to the internal energy change ∆𝑈 rather than to ∆𝐻. The enthalpy change is calculated according to
the formula
∆𝐻 = 𝑞𝑣 + ∆𝑛𝑔𝑅𝑇
in which ∆𝑛𝑔 is the change in the number of moles of gases in the reaction.

EXAMPLE PROBLEM
The temperature of a calorimeter increases 0.10 K when 7.52 J of electric energy is used to heat it.
What is the heat capacity of the calorimeter?

SOLUTION:
7.52
𝐶= = 75.2 𝐽/𝐾
0.10

EXAMPLE PROBLEM
When a 10.0-watt (J/s) heater is used to heat a bomb calorimeter, its temperature increases by 3.0 K
in 5.0 min. Calculate the heat capacity of the calorimeter.

SOLUTION:
Energy used = 10 * 5 * 60 = 3000J
Thus, C = 3000 / 3.0 = 1000 J/K,
This is equivalent to (1000 J/K) / (75.52 J/K mol) = 13.3 moles of water.

RVM Lecture Manual: Physical Chemistry 1 3

EXAMPLE PROBLEM
A calorimeter with heat capacity equivalent to having 13.3 moles of water is used to measure the
heat of combustion from 0.303 g of sugar (C12H22O11). The temperature increase was found to be 5.0 K.
Calculate the heat released and the amount of heat released by 1.0 g, and 1.0 mole of sugar.

SOLUTION:
Heat released, qv,
qv = 13.3 mol * 75.2 J/(Kmol) * 5.0 K = 5000J
The amount of heat released by 1.0 g would be,
5000 J/0.303 g = 16.5 kJ / g
16.5kJ / g * 342.3 g/mol = 5648 kJ/mol

EXAMPLE PROBLEM
The heat released by one mole of sugar from a bomb calorimeter experiment is 5648 kJ/mol.
Calculate the enthalpy of combustion per mole of sugar.

SOLUTION:
C12H22O11(s) + 12 02(g) = 12 CO2(g) + 11 H2O(l)
dH = dE = 5648 kJ/mol

EXAMPLE PROBLEM
When 0.1025 g of benzoic acid was burnt in a bomb calorimeter the temperature of the calorimeter
increased by 2.1650C. for benzoic acid dH0comb = -3227 kJ mol-1. Calculate the heat capacity of the calorimeter.

SOLUTION:
C7H6O2(s) + 7.5 O2(g)→ 7CO2(g) + 3H2O(l), dH0 = 3227 kJ

𝑃𝑉 = ∆𝑛𝑅𝑇, where ∆𝑛 = 7 − 7.5 = −0.5 𝑚𝑜𝑙

∆𝐸 = ∆𝐻 − ∆𝑛𝑅𝑇 = −3227 − (-0.5 x 8.314 x 298) = -3226 kJ/mol
0.0125
𝑞= mol x 3226 kJ/mol = 2.680 kJ
112.13
𝑄 2.680
𝐶= = = 1.238 𝑘𝐽/𝐾
𝑑𝑇 2.165
_____________________________________________________________________________________________________________________

(b.) DEFINITION OF HEAT CAPACITY

The amount of heat required to raise the temperature of any substance by 1 Kelvin is known as heat
capacity, and is given the symbol Cp, the unit at SI is J/K. The word specific before the name of any extensive
physical quantity refers to the quantity per mass. The term specific heat capacity refer to the amount of heat
required to raise the temperature of unit mass of material per 1 Kelvin, the unit at SI is J/K kg.

Isochoric Process
The heat capacity related to process occurring at constant volume is denoted by C v and is defined by
𝑑𝑄𝑣
𝐶𝑉 =
𝑑𝑇
The heat is supplied at constant volume. Since Q v is equal to U at constant volume then
𝑑𝑈
𝐶𝑣 = ( )
𝑑𝑇

Isobaric Process
The heat capacity related to the process occurring at constant pressure is C p and defined by

RVM Lecture Manual: Physical Chemistry 1 4

 𝑑𝑄𝑃 𝑑𝐻
𝐶𝑝 = ( )=( )
𝑑𝑇 𝑑𝑇
By arrangement of the formula obtain in isochoric and isobaric process, we can obtain the formulas

At isochoric:
𝑑𝑈 𝑑𝑄𝑣
𝐶𝑉 = =
𝑑𝑇 𝑑𝑇
𝑇2
𝑄𝑉 = ∫ 𝐶𝑉 𝑑𝑇
𝑇1
𝑄𝑉 = 𝐶𝑉 (𝑇2 − 𝑇1 ) = ∆𝑈
At isobaric:
𝑑𝐻 𝑑𝑄𝑃
𝐶𝑃 = =
𝑑𝑇 𝑑𝑇
𝑇2
𝑄𝑃 = ∫ 𝐶𝑃 𝑑𝑇
𝑇1
𝑄𝑃 = 𝐶𝑃 (𝑇2 − 𝑇1 ) = ∆𝐻

For solid and liquid, ∆𝑈 and ∆𝐻 are very close to each other. For consequently, C vm and Cpm at mole
unit are essentially the same for solid and liquid. For gases however, the ∆(𝑃𝑉) term is appreciable and there
is a significant difference between Cvm and Cpm. For ideal gas, this obeys:
𝑃𝑉 = 𝑛𝑅𝑇
The relationship between Cv and Cp can be derived as follows, assume at 1 mole of gas
𝐻𝑚 = 𝑈𝑚 + 𝑃𝑉𝑚 = 𝑈𝑚 + 𝑅𝑇
𝑑𝐻𝑚 𝑑𝑈𝑚 𝑑𝑅𝑇
= +
𝑑𝑇 𝑑𝑇 𝑑𝑇
𝑑𝑅𝑇
𝐶𝑝,𝑚 = 𝐶𝑣,𝑚 +
𝑑𝑇
𝐶𝑝,𝑚 = 𝐶𝑣,𝑚 + 𝑅

6.2. DEFINITION OF ENTHALPY

The relationship suggests that it would be convenient to give a name to the quantity U + PV, and
known as enthalpy with the symbol H
𝐻 = 𝑈 + 𝑃𝑉
This equation is valid only if the work is all PV work. Under these circumstances the increase in the
change in enthalpy ∆𝐻 is equal to the heat dQ supplies at constant pressure. Since U, P and V are all state
function, enthalpy is also a state function.

ENTHALPY
Enthalpy is a convenient state function, since it lumps together changes in energy in the system as
well as changes in energy resulting from volume changes.
For a system that changes volume, the internal energy is not equal to the heat supplied, as for a fixed
volume system.
Some energy supplied as heat to the system returns to surroundings as expansion work: dU < dq,
because dU = dq + dw
When heat is supplied to the system at a constant pressure (e.g., reaction containers open to
atmosphere), another thermodynamic state function known as enthalpy, H, can be measured accurately:
H = U + pV
Change in enthalpy is equal to heat supplied to the system at constant pressure
dH = dQ ∆𝐻 = 𝑞𝑝

ENTHALPY: WHY DOES ∆𝑯 = 𝑸𝒑 ?

1. Infinitesimal change in state of system: U changes to U + dU, p changes to p + dp, V changes to V +
dV, so H = U + pV becomes

RVM Lecture Manual: Physical Chemistry 1 5

 H + dH = (U + dU) + (p + dP) (V + dV)
= U + dU +pV +pdV +VdP +dPdV
2. The product of two infinitesimal quantities, dPdV, disappears.
Since H = U + pV, we write:
H + dH = H +dU + pdV + VdP
dH = dU + pdV + VdP
3. Substitute in dU = dq + dw
dH= dQ + dW + pdV + VdP
4. System is in mechanical equilibrium with surroundings at pressure
p, so there is only expansion work (dw = -pdV)
dH = dQ + VdP
5. Impose condition that heating is done at constant pressure, so dp
=0
dH = dQ

6.3. MEASUREMNT OF CHANGE IN ENTHALPY, ∆𝑯

An adiabatic bomb calorimeter or an adiabatic flame calorimeter can be used to measure ∆H by
watching the ∆T that happens as the result of physical or chemical changes occurring at constant pressure.
The adiabatic flame calorimeter measures ∆𝑇 resulting from combustion of a substance in O2 (g).
At constant pressure and element is immersed in a T-controlled water bath - combustion occurs when
a known amount of reactant is burned, and ∆T is then monitored.
The adiabatic bomb calorimeter measures ∆U during a change, from which ∆H can be calculated (in
this case, solids and liquids have such small molar volumes that 𝐻𝑚 = 𝑈𝑚 + 𝑝𝑉𝑚 ≈ 𝑈𝑚 ).
Processes are accompanied by a very small ∆V, so there is negligible work done on surroundings.

6.4. RELATION OF INTERNAL ENERGY AND ENTHALPY

For a perfect gas, the internal energy and enthalpy can be related by:
H = U + pV = U + nRT
For a measureable change in enthalpy: ∆𝐻 = ∆𝑈 + ∆𝑛𝑔𝑎𝑠 𝑅𝑇 where ∆ngas is the change of moles of
gas in the reaction.

EXAMPLE PROBLEM:
2 𝐻2 (𝑔) + 𝑂2 (𝑔) → 2 𝐻2 𝑂 (𝑙) ∆𝑛𝑔𝑎𝑠 = −3 𝑚𝑜𝑙
∆𝐻 − ∆𝑈 = (−3𝑚𝑜𝑙)𝑥 𝑅𝑇 = − 7.5 𝑘𝐽

Why is the difference negative?

Heat escapes from system, during reaction, but the system contracts as the liquid is formed (energy is
restored from the surroundings)

6.5. MECHANICAL DEFINITION OF HEAT

Imagine that our system is not purely adiabatic (thermal insulation is not very good). The change in
U, the internal energy, may be the same before (state function), but more work is required to make the same
kind of change in energy:
e.g., 42 kJ of work is done in an adiabatic container; however, to achieve the same change of
state in a diathermic container: 50 kJ of work is required
The system is absorbing heat if Q > 0 Q = Wad - W
Q = 42 kJ - 50 kJ = -8 kJ (8 kJ is lost from the system as heat)
Since ΔU is by definition equal to Wad, the expression for energy transferred to a system as heat is
which is the same as the expression for the First Law, ΔU = Q + W

RVM Lecture Manual: Physical Chemistry 1 6

6.6. HEAT CAPACITY AND INTERNAL ENERGY
Here is a plot of the internal energy of a system versus temperature.

The slope of the curve at a given temperature is defined as the heat capacity of the system.
The heat capacity at constant volume is formally defined as:
𝜕𝑈
Cv = ( )𝑉
𝜕𝑇
The RHS is a partial derivative, which is a derivative where all variables are held constant except for
one - it gives the slope of the plot of U vs. T.
The heat capacity at temperature A is lower than that at temperature B.
Increasing temperature increases the internal energy of a system. The exact increase depends upon
the heating conditions. Heat cannot be detected or measured directly. (There is no “heat meter”.) One way to
determine the magnitude of a heat transfer is to measure the work needed to bring about the same change in
the thermodynamic state of the system as was produced by heat transfer.
Another approach is to deduce the magnitude of a heat transfer from the its effects; namely, a
temperature change. The temperature change resulting from a particular transfer of heat is determined by the
heat capacity of the system, which is defined as follows:
Heat capacity (of a system): the heat required to raise the temperature of the system by one Kelvin
(or one °C). It is an extensive property.

6.7. MOLAR HEAT CAPACITY

Heat capacity is an extensive property: for instance, we know for instance that 100 g of water has 100x
the heat capacity of 1 g of water.
So, we can also have an intensive property, the molar heat capacity at constant volume, which is a
measure of heat capacity at constant volume per mole of material: Cv,m.
𝑆
There is also the specific heat capacity, 𝐶𝑉𝑚 , which gives us a useful measure of heat capacity per unit
mass of the sample.
Generally:
Heat capacities are temperature dependent, decreasing at lower T.
Over small ranges near room temperature, CV are almost invariant to changes in temperature.

6.8. RELATING U AND T AT CONSTANT V

Heat capacity is used (say in a calorimeter) to relate internal energy changes and changes in
temperature.
As usual, an infinitesimal change in temperature changes energy slightly:
dU = CvdT at constant volume
Over a measurable range of temperatures
ΔU = CvdT at constant volume

Change in energy can be noticed with heat supplied at a constant V

RVM Lecture Manual: Physical Chemistry 1 7

 Qv = CvdT
1. Supply a controlled known amount of heat to the sample (say with an electric current in a heater
2. Monitor the resulting increase in temperature
3. The ratio: heat supplied/temperatureincrease is the heat capacity

Large heat capacity: large supply of heat, small change in measured T

Small heat capacity: small supply of heat, large change in measured T
Infinite heat capacity: at a phase transition, energy changes phases

EXERCISES:

1. Liquid water at 180℃ and 1002.7 kPa has an internal energy of 762 kJ/kg and a specific volume of 1.128
cm3/g.
a. What is its enthalpy?
b. The water is brought to vapor state at 300℃ and 1500kPa where its internal energy is 2784.4 kJ/kg
and its specific volume is 169.7 cm3/g. Calculate ∆𝑈 and ∆𝐻 for this process.
2. An average man weighs about 70 kg and produces about 10460 kJ of heat per day.
a. Suppose that a man were an isolated system and that his heat capacity were 4.18J/Kg; if his
temperature were 37℃ at a given time, what would be his temperature 24 h later?
b. A man is in fact an open system, and the main mechanism for maintaining his temperature constant
is evaporation of water. If the enthalpy of vaporization of water at 37℃ is 43.4 kJ/mol, how much
water needs to be evaporated per day to keep the temperature constant?
3. When 2.25mg of anthracene, C14H10 (s) was burned in a bomb calorimeter the temperature rose by 1.35
K. Calculte the calorimeter constant. By how much will the temperature rise when 135 mg of phenol,
C6H5OH (s) is burned in the calorimeter under the same conditions? ∆𝐻𝑐 of C14H10 (s) = 7016 kJ/mol
4. Calculate the amount of heat required to raise the temperature of 20 g of water vapor from 250℃ to
400℃.
5. A 55.00 g piece of metal was heated in boiling water to 99.8℃ and then dropped into water in an
insulated beaker. There is 225 mL of water (density = 1.00 g/mL) in the beaker, and its temperature
before the metal was dropped in was 21℃. The final temperature of the metal and water is 23.1℃. What
is the specific heat of the metal in J/gK? Assume that the heat required to warm the walls of the beaker
from 21.0℃ to 23.0℃ is negligible and no heat transfers to the atmospheres.
6. A bomb calorimeter is used to determine thermal properties. Calculate the molar enthalpy of the
combustion of glucose when 2.22 g of glucose are ignited and water (1.2 kg) in the well-insulated
calorimeter rises in temperature from 18℃ to 23.19℃. Assume that the water absorbs all heat given off.
7. Calculate the flow rate of benzene that can be heated from 25.0℃ to 80.0℃ by heat exchange with 100
kg/hr of saturated steam that condenses at 100℃. Assume that the average specific heat capacity of
benzene from 25℃ to 80.0℃ is 142.94 J/molK.
8. Two liquid enter a mixing chamber and are discharged at 80.0℉ at the rate of 50 gal/min. Liquid A enters
at 140.0℉ with a specific heat of 10 BTU/gal℉. Liquid B enters at 65.0℉ with the specific heat of 8.33
BTU/gal℉. What is the volume flow of liquid B?
9. When a reaction that was known to release 17.55 kJ of heat took place in a calorimeter and containing
100 mL of water, the temperature rose by 3.65℃. When 50 mL of HCl was mixed with 50 mL of aqueous
NaOH solution in the same container, the temperature rose by 1.15℃. How much heat was released by
the neutralization reaction?
10. The expression for ∆𝐻° of formation of CO2 as a function of temperature is ∆𝐻𝑜 = -93480 – 0.603 T –
0.675 x 10-4 T2 - 1.091 x 105/T. Find the ∆𝐶𝑝𝑜 for this reaction as a function of T.

RVM Lecture Manual: Physical Chemistry 1 8