THERMOCHEMISTRY

Enthalpy of Chemical Reactions and Thermochemical

Equations
 SPECIFIC LEARNING OUTCOMES
At the end of the lesson, the learners will be able to:
• Describe and explain how heat of reactions are determined by calorimetry;
• Determine the heat of neutralization of an acid
• Explain enthalpy of a reaction.
• Write the thermochemical equation for a chemical reaction.
• Calculate the change in enthalpy of a given reaction using Hess Law.
DEFINITION OF TERMS

Enthalpy (H)
 A thermodynamic quantity used to describe heat changes (q) taking place at
constant pressure.
Enthalpy or Heat of reaction (ΔH)
 Differences between the enthalpies of the products and the enthalpies of
the reactants.
ENTHALPY OF CHEMICAL REACTIONS

• Our next step is to see how the first law of thermodynamics can be applied to
processes carried out under different conditions.
• Specifically, we will consider a situation in which the volume of the system is kept
constant and one in which the pressure applied on the system is kept constant.
• These are commonly encountered cases in the laboratory.
• If a chemical reaction is run at constant volume, then ΔV = 0 and no P-V work will
result from this change.
ΔE = q + w since w = -PΔV
ΔE = q - P ΔV when ΔV = 0
ΔE = q v
• We add the subscript “v” to remind us that this is a constant-volume process.
 ENTHALPY
• Constant-volume conditions are often inconvenient and sometimes impossible to
achieve.
• Most reactions occur under conditions of constant pressure (usually atmospheric
pressure).
• If such a reaction results in a net increase in the number of moles of a gas, then the
system does work on the surroundings (expansion).
• This follows from the fact that for the gas formed to enter the atmosphere, it must
push the surrounding air back.
• Conversely, if more gas molecules are consumed than are produced, work is done on
the system by the surroundings (compression).
• Finally, no work is done if there is no net change in the number of moles of gases
from reactants to products.
• In general, for a constant-pressure process we write
ΔE = q + w since w = -PΔV and P is constant
ΔE = q p - P ΔV
• Rearrange the equation to find qp
q p = ΔE + P Δ V subscript “p” denotes constant-pressure condition
• For a constant-pressure process, qp = H
qp = H = E + PV
H = E + PV
where E is the internal energy of the system
P and V are the pressure and volume of the system
• For any process, the change in enthalpy according to equation is given by
ΔH = ΔE + Δ(PV) If the pressure is held constant, then
ΔH = Δ E + P ΔV
• We now have two quantities—ΔE and Δ H—that can be associated with a
reaction.
• Both quantities measure energy changes, but under different conditions.
• If the reaction occurs under constant-volume conditions, then the heat change, qv,
is equal to Δ E.
ΔE = q v - P ΔV when ΔV = 0
ΔE = q v
• On the other hand, when the reaction is carried out at constant pressure, the heat
change, qp, is equal to Δ H. qp = H
ENTHALPY OF REACTIONS (ΔH)
• Because most reactions are constant-pressure processes, we can equate the heat
change in these cases to the change in enthalpy. For any reaction of the type
reactants → products
• We define the change in enthalpy, called the enthalpy of reaction, ΔH, as the
difference between the enthalpies of the products and the enthalpies of the
reactants:
ΔH = H(products) - H(reactants)
• The enthalpy of reaction (ΔH) can be positive or negative, depending on the process.
 For an endothermic process (heat absorbed by the system from the
surroundings), ΔH is positive (that is, Δ H > 0).
 For an exothermic process (heat released by the system to the surroundings),
ΔH is negative (that is, ΔH <0).
• A positive value of ΔH reflects a increase in enthalpy of the system as a result of an
endothermic process.
• A negative value of ΔH reflects a decrease in enthalpy of the system as a result of
an exothermic process.
 THERMOCHEMICAL EQUATIONS
• At 0oC and a pressure of 1 atm, ice melts to form liquid water.
• Measurements show that for every mole of ice converted to liquid water under
these conditions, 6.01 kilo-joules (kJ) of heat energy are absorbed by the system
(ice).
• Because the pressure is constant, the heat change qp is equal to the enthalpy
change, ΔH.
• Furthermore, this is an endothermic process, as expected for the energy-absorbing
change of melting ice.
• Therefore, ΔH is a positive quantity.
• The equation for this physical change is
H2O(s) → H2O(l) ΔH = 6.01 kJ/mol
• As another example, consider the combustion of methane (CH4), the principal
component of natural gas:
CH4(g + 2O2(g) → CO2(g) + 2H2O(l) ΔH= -890.4 kJ/mol
• To change ice to liquid, we need to add heat, so it is an endothermic process.
• From experience, we know that burning natural gas releases heat to the
surroundings, so it is an exothermic process.
• The equations for the melting of ice and the combustion of methane are examples
of Thermochemical Equations, which show the enthalpy changes as well as the
mass relationships.
• It is essential to specify a balanced equation when quoting the enthalpy change of
a reaction.
The following guidelines are helpful in writing and interpreting thermochemical
equations:
1. When writing thermochemical equations, we must always specify the physical
states of all reactants and products, because they help determine the actual
enthalpy changes. For example, in the equation for the combustion of methane, if
we show water vapor rather than liquid water as a product,
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH = -890.4 kJ/mol
the enthalpy change is -802.4 kJ rather than -890.4 kJ because 88.0 kJ are needed to
convert 2 moles of liquid water to water vapor;
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) ΔH = -802.4 kJ/mol

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH = -890.4 kJ/mol

2H2O(l) → 2H2O(g) ΔH = 88.0 kJ/mol
total ΔH ΔH = -802.4 kJ/mol
2. If we multiply both sides of a thermochemical equation by a factor n, then ΔH
must also change by the same factor. Thus, for the melting of ice, if n = 2, we
have
H2O(s) → H2O(l) ΔH = 6.01 kJ/mol

H2O(s) → 2H2O(l) ΔH = 2(6.01 kJ/mol) = 12.0 kJ/mol

3. When we reverse an equation, we change the roles of reactants and products.
Consequently, the magnitude of ΔH for the equation remains the same, but its
sign changes.
H2O(s) → H2O(l) ΔH = 6.01 kJ/mol
H2O(l) → H2O(s) ΔH = -6.01 kJ/mol

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH = -890.4 kJ/mol

CO2(g) + 2H2O(l) → CH4(g) + 2O2(g) ΔH = 890.4 kJ/mol
• and what was an endothermic process becomes exothermic, and vice versa.
EXAMPLE

Given the thermochemical equation

SO2(g) + O2(g) → SO3(g) ΔH = -99.1 kJ/mol

Calculate the heat evolved when 74.6 g of SO2 (molar mass = 64.07 g/mol) is
converted to SO3.
SOLUTION:
SO2(g) + O2(g) → SO3(g) ΔH = -99.1 kJ/mol
The thermochemical equation shows that for every mole of SO2 burned, 99.1 kJ of
heat are given off (note the negative sign)

grams of SO2 → moles of SO2 → kilojoules of heat generated

Therefore, the heat produced is given by

-
PRACTICE

1. Calculate the heat evolved when 266 g of white phosphorus (P4) burns in air
according to the equation (P – 30.97 g)
P4(s) + 5O2(g) → P4O10(s) ΔH = - 3013 kJ/mol

2. Determine the amount of heat (in kJ) given off when 1.26 x 104 g of NO2 are
produced according to the equation .
(N – 14.01 g, O – 16.00g)
2NO(g) + O2(g) → 2NO2(g) ΔH = -114.6 kJ/mol
 A COMPARISON OF ΔH AND ΔE
• What is the relationship between ΔH and ΔE for a process?
• To find out, let us con-sider the reaction between sodium metal and water:
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g) ΔH = -367.5 kJ/mol
• This thermochemical equation says that when two moles of sodium react with an
excess of water, 367.5 kJ of heat are given off. Note that one of the products is
hydrogen gas, which must push back air to enter the atmosphere.
• Consequently, some of the energy produced by the reaction is used to do work of
pushing back a volume of air (ΔV) against atmospheric pressure (P).
• To calculate the change in internal energy, we rearrange Equation as follows:
ΔE = ΔH - P ΔV
• If we assume the temperature to be 25oC and ignore the small change in the volume
of the solution, we can show that the volume of 1 mole of H2 gas at 1.0 atm and
298 K is 24.5 L, so that - PΔV = -24.5 L ·atm or -2.5 kJ.
 ΔE = ΔH - PΔV
= - 367.5 kJ/mol - 2.5 kJ
= - 370.0 kJ/mol
• This calculation shows that ΔE and ΔH are approximately the same.
• The reason ΔH is smaller than ΔE in magnitude is that some of the internal energy
released is used to do gas expansion work, so less heat is evolved.
• For reactions that do not involve gases, ΔV is usually very small and so ΔE is
practically the same as ΔH .
• Another way to calculate the internal energy change of a gaseous reaction is to
assume ideal gas behavior and constant temperature. In this case,
ΔE = ΔH - Δ(PV) since PV = nRT
ΔE = ΔH - Δ(nRT)
ΔE = ΔH - RTΔn

Where Δn = moles of product gases - moles of reactant gases

R = 8.314 J/ K ·mol
EXAMPLE

Calculate the change in internal energy in kJ when 2 moles of CO are converted to 2

moles of CO2 at 1 atm and 25oC:
2CO(g) + O2(g) → 2CO2(g) ΔH = -566.0 kJ/mol
SOLUTION
2CO(g) + O2(g) → 2CO2(g) ΔH = -566.0 kJ/mol

Δn = moles of product gases - moles of reactant gases

= 2 – ( 2 + 1)
= - 1
ΔE = ΔH - RTΔn

= - 563.5 kJ/mol
CALORIMETRY

• In the laboratory, heat changes in physical and chemical processes are measured
with a calorimeter, a closed container designed specifically for this purpose.
• Our discussion of calorimetry, the measurement of heat changes, will depend on
an understanding of specific heat and heat capacity, so let us consider them first.
Specific Heat (s)

• It is the amount of heat required to raise the temperature of one gram of the
substance by one degree Celsius.
• It is an intensive property,

Heat Capacity (C)

• It is the amount of heat required to raise the temperature of a given quantity of

the substance by one degree Celsius.
• It is an extensive property.

C = ms where m is mass in grams

• For example, the specific heat of water is 4.184 J/g·oC, and what is the heat
capacity of 60.0 g of water is
C = ms
= (60.0 g)(4.184 J/g·oC)
= 251.04 J/oC
• If we know the specific heat and the amount of a substance, then the change in
the sample`s temperature (Δt) will tell us the amount of heat (q) that has been
absorbed or released in a particular process. The equations for calculating the
heat change are given by:
q = ms Δt since C = ms
q = CΔt
Where Δt = tfinal - tinitial
EXAMPLE

A 466-g sample of water is heated from 8.50oC to 74.60oC. Calculate the

amount of heat absorbed (in kJ) by the water.
(sH20 = 4.184 J/g ·oC)
SOLUTION
q = ms Δt
= (466 g)(4.184 J/g ·oC)((74.60oC - 8.50oC)
= 128,878.08 J
PRACTICE

1. An iron bar of mass 869 g cools from 94C to 5C. Calculate the heat released (in
kilojoules) by the metal. (sFe = 0.444 J/g ·oC)
2. A piece of silver of mass 362 g has a heat capacity of 85.7 J/oC. What is the
specific heat of silver?
3. Calculate the amount of heat liberated (in kJ) from 366 g of mercury when it cools
from 77.0oC to 12.0oC. (sHg = 0.139J/g ·oC)
 Constant-Volume Calorimetry

• Heat of combustion is usually measured by placing a known mass of a compound in

a steel container called a constant-volume bomb calorimeter, which is filled with
oxygen at about 30 atm of pressure.
• Constant volume” refers to the volume of the container, which does not change
during the reaction. Note that the container remains intact after the measurement.
The term “bomb calorimeter” connotes the explosive nature of the reaction (on a
small scale) in the presence of excess oxygen gas.
 qsystem = qcal + qrxn
• where qcal and qrxn are the heat changes for the calorimeter and the reaction,
respectively. Thus,
qrxn = - qcal
• To calculate qcal, we need to know the heat capacity of the calorimeter (Ccal) and the
temperature rise, that is
qcal = CcalΔt
• The quantity Ccal is calibrated by burning a substance with an accurately known
heat of combustion.
• For example, it is known that the combustion of 1 g of benzoic acid (C6H5COOH)
releases 26.42 kJ of heat. If the temperature rise is 4.673oC, then the heat
capacity of the calorimeter is given by

Ccal = 5.65 kJ/oC

EXAMPLE

A quantity of 1.435 g of naphthalene (C10H8), a pungent-smelling substance used in

moth repellents, was burned in a constant-volume bomb calorimeter. Consequently,
the temperature of the water rose from 20.28oC to 25.95oC. If the heat capacity of
the bomb plus water was 10.17 kJ/oC, calculate the heat of combustion of
naphthalene on a molar basis; that is, find the molar heat of combustion.
EXAMPLE

• Compute for Ccal

Since qsystem = qcal + qrxn

qrxn = - qcal
qrxn = - 57.66 kJ
• Then
 Constant-Pressure Calorimetry
• A simpler device than the constant-volume calorimeter is the constant-pressure
calorimeter, which is used to determine the heat changes for noncombustion
reactions. A crude constant-pressure calorimeter can be constructed from two
Styrofoam coffee cups, as shown in the figure.
• This device measures the heat effects of a variety of reactions, such as acid-base
neutralization, as well as the heat of solution and heat of dilution.
• Because the pressure is constant, the heat change for the process (qrxn) is equal to
the enthalpy change (ΔH). As in the case of a constant-volume calorimeter, we treat
the calorimeter as an isolated system. Furthermore, we neglect the small heat
capacity of the coffee cups in our calculations.
EXAMPLE
SOLUTION

Since qPb + qH2O = 0

qPb = - qH2O
The heat gained by the water is given by
qH2O = msΔt
Because the heat lost by the lead pellet is equal to the heat gained by the water,
so qPb = -280.3 J. Solving for the specific heat of Pb, we write
STANDARD ENTHALPY OF FORMATION AND REACTION

• Many compounds cannot be directly synthesized from their elements.

• In some cases, the reaction proceeds too slowly, or side reactions produce
substances other than the desired compound.
• In these cases, ΔHof can be determined by an indirect approach, which is based on
Hess’s law of heat summation, or simply Hess’s law, named after the Swiss chemist
Germain Hess.
• Hess` s law can be stated as follows:
 When reactants are converted to products, the change in enthalpy is the same
whether the reaction takes place in one step or in a series of steps.
• In other words, if we can break down the reaction of interest into a series of
reactions for which ΔHorxn can be measured, we can calculate ΔHorxn for the overall
reaction.
• Hess`s law is based on the fact that because H is a state function, ΔH depends
only on the initial and final state (that is, only on the nature of reactants and
products). The enthalpy change would be the same whether the overall reaction
takes place in one step or many steps.
• Let`s say we are interested in the standard enthalpy of formation of carbon
monoxide (CO). We might represent the reaction as
• However, burning graphite also produces some carbon dioxide (CO2), so we cannot
measure the enthalpy change for CO directly as shown.
• Instead, we must employ an indirect route, based on Hess`s law. It is possible to
carry out the following two separate reactions, which do go to completion:

(a)
(b)
We will reverse equation (b)

(c)

Because chemical equations can be added and subtracted just like algebraic
equations, we carry out the operation (a) + (c) and obtain

(a)
(c)

ΔHof(CO) = -110.5 kJ/mol.

• The general rule in applying Hess`s law is to arrange a series of chemical equations
(corresponding to a series of steps) in such a way that, when added together, all
species will cancel except for the reactants and products that appear in the overall
reaction.
• This means that we want the elements on the left and the compound of interest on
the right of the arrow. Further, we often need to multiply some or all of the
equations representing the individual steps by the appropriate coefficients.
EXAMPLE
SOLUTION

Multiply equation (a) by 2

(d)

Reverse equation (c) and divide the equation and ΔHorxn by the coefficient of C2H2.

(e)
Adding Equations (d), (b), and (e) together, we get

(d)
(b)
(e)

ΔHof(C2H2) = 226.6 kJ/mol.

EVALUATION:
1. Calculate the standard enthalpy of formation of carbon disulfide (CS2) from its elements, given
that

C(graphite) + 2S(rhombic) → CS2(l)

2. Consider the reaction: H2(g) + Cl2(g) → 2HCl(g) ΔH= -184.6 kJ/mol If 3 moles of H2
react with 3 moles of Cl2 to form HCl, calculate the work done against a pressure of 1.0 atm at
25oC. What is ΔE for this reaction? Assume the reaction goes to completion.