Chem 101 – Lecture Notes for Chapter 6: Thermochemistry

In Chapter 6 you are responsible for sections 6.1-6.6, we do not cover 6.7.

This chapter is concerned with energy changes in chemical reactions. Thermochemistry, the
study and measurement of heat effects of chemical reactions is a branch of thermodynamics,
the science of energy, heat and work.

1 Energy, heat and work (Chang sections 6.1, 6.2 and 6.3, pp. 224-232)

Energy can be in a number of forms including:

Thermal energy (related to the temperature of a system)
Chemical energy (the energy stored in the chemical bonds of a molecule)
Potential energy (e.g. gravitational energy)
Radiant energy, the energy contained in electromagnetic waves (light, infra red radiation,
UV radiation, etc.).

Energy, heat and work are expressed in the same unit, the joule, symbol J. We have
already seen in Chapter 5 that:
work (J) = force(N) x distance over which the force acts (m),
or:
w = F.d J = N.m

The unit of heat energy formerly was the calorie, cal:

1 calorie is the amount of heat needed to raise the temperature of 1 g water by 1 oC.
(Raising the temperature by 1 oC is the same as raising the temperature by 1 K).

The relation between the calorie and the joule has to be determined by experiment, it is
not one of “nature’s constants”. In fact, the first scientist to try and measure the
equivalency of heat and work was no other than ….. Mr. Joule! The exact conversion
factor was determined long after Joule’s efforts:

1 cal = 4.184 J

From the definition of the calorie above, we recognize that the calorie is in fact the
specific heat of water:

The specific heat, s, is the amount of heat necessary to increase the temperature of 1 g
substance by 1 oC (or by 1 K).
For instance; the specific heat of water, s(H2O(l)) = 4.184 J/g.K
The specific heat of copper metal, s(Cu(s)) = 0.385 J/g.K

The heat capacity, C , of a substance is the amount of heat needed to increase the
temperature of a given quantity of substance by 1 oC (or 1 K). C has the units J/K
The heat (symbol q) needed to raise m grams of substance from T1 to T2 is:
q = s.m.(T2 − T1) = s.m.ΔT
The heat needed to raise the temperature of an object with heat capacity C from T1 to T2
is:
q = C(T2 − T1) = CΔT

Examples.
1. How much heat is needed to raise the temperature of 1000 g water from 20 oC to
100 oC?
Answer.
q = s.m.ΔT = 4.184(J/K.g)x1000(g)x80(K) = 3.35x103 J or 3.35 kJ
Note that for temperature differences ΔT in oC and K is the same!

2. How much heat is released when a piece of copper, Cu, weighing 95 g is cooled from
400 oC to 27 oC? The specific heat of Cu(s) = 0.385 J/g.K.
Answer.
q = s.m.ΔT = 0.385(J/g.K)x95(g)x(−373)(K) = −1.36x104 J or −13.6 kJ
Note that in this case q is indeed negative, the heat is given off to the environment (and
lost by the system, i.e., the copper)

Heat, work and the first law of thermodynamics

The first law of thermodynamics states that:

different forms of energy can be converted into each other, but the total energy (i.e., the
sum of all different forms of energy) must be conserved, it cannot be created or
destroyed.

In chemical systems, we are concerned with heat and work as the forms of energy. Then
the first law of thermodynamics can be written in equation form as:

ΔE = q + w

Where: q = the heat added to a system

w = the work added to the system
ΔE is the change in energy of the system

In other words, the first law in equation form expresses that when we add heat to a
system, or add work to a system (“do work on the system”), the energy of the system
must increase by exactly the amount of heat and work added. This is most easily seen if
ΔE, q, and w all are expressed in J.

In the first law, the ‘work term” w is often in the form of “pressure-volume work”, it is
the work we do (added to the system) when we compress a gas, or the work the system
does (lost to the system) when a gas expands against an external pressure. Without
detailed proof:
w = −pΔV

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We can demonstrate this equality by dimensional analysis:
w = −pΔV units Pa.m3 = N.m−2.m3 = N.m = J
When we substitute this in the first law we have;
ΔE = q −pΔV

The energy E of a system is a “State Function”, which means that however we add or
take away heat or work from the system, the energy change depends only on the initial
and final states (p,V,T) of the system, not on how we added or took away the heat or
work.

Heat effects in chemical reactions, enthalpy

In chemical reactions, some chemical bonds are broken, others are made. For instance, in
the reaction:
2H2(g) + O2(g) → 2H2O(g)
we break 2 H−H bonds and 1 O=O bond, and we make 4 O−H bonds. The difference in
chemical energy of these changes in bonds causes a certain amount of energy to be
released as heat, the heat of reaction or qrxn. For the case of the formation of H2O(g) from
its elements hydrogen and oxygen, the heat released is very large, 242 kJ per mole of H2O
formed (1 kJ = 1000 J).

A reaction in which heat is released (given off to the environment) is called an

exothermic reaction. Because the system losses this heat, we give q a negative sign, and
write:
2H2(g) + O2(g) → 2H2O(g) q = −484 kJ

It is −484 because the reaction as written forms 2 moles of H2O(g), so the heat released
equals 2x(−242) = −484 kJ.

On the other hand, for the reaction:

Ag2O(s) → 2Ag(s) + ½O2(g) q = +31 kJ
The positive sign means that energy has to be added to the system in order for this
reaction to take place. This is called an endothermic reaction.

Exothermic process: heat is released from the system to the environment, qrxn = −
Endothermic process: heat is added from the environment to the system, qrxn = +

In many reactions carried out in the laboratory or in nature (e.g. biochemical systems),
the reaction takes place at constant pressure (typically 1 atm). When the pressure is
constant, we add the subscript p to qp:

qp = the heat effect of a reaction carried out at constant pressure.

The next definition is that of e new thermodynamic function, the enthalpy H:

H = E + pV

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For reactions or processes at constant pressure, this equation is written as:

ΔH = ΔE + pΔV

This is the the relation between the energy change, ΔE (think of the changes in chemical
bonds), and the enthalpy change ΔH for a chemical reaction or physical change.

More importantly, since at constant pressure the first law states that ΔE = qp −pΔV. This
tells us why we defined enthalpy this way:

ΔH = qp

When we observe a heat effect of a chemical or physical change in an open, constant

pressure system in the laboratory, or in a biological system, the enthalpy change is simply
the observed heat effect!

In thermochemistry, we write chemical or physical processes together with their enthalpy

change (their heat effect), and we have the same sign convention:

Exothermic process: (heat is released to the environment): qp = ΔH = −ve

Endothermic process (heat is taken up by the system): qp = ΔH = +ve

Some examples of how we write the full reaction for thermochemical processes:

N2(g) + 3H2 → 2NH3(g) ΔH = − 92.6 kJ/mol, an exothermic reaction

H2O(l) → H2O(g) ΔH = + 44.0 kJ/mol, an endothermic process
Note that we always express the enthalpy change for the reaction as written as kJ/mol: in
the first reaction for 1 mol N2 reacting with 3 mol H2 to form 2 mol NH3.

The change in enthalpy, ΔH of such a chemical or physical change equals the difference
in enthalpy (heat content) of the products and reactants:
ΔH = H(products) − H(reactants)

Examples
1. Calculate the enthalpy change (heat effect), when 5.6 g N2 reacts with excess
hydrogen to produce NH3.
Answer.
From the reaction above, we see that when 1 mol of N2 reacts, ΔH = − 92.6 kJ/mol.
Therefore:
1 mol N 2 −92 . 6 kJ
5 .6 g N 2 x x =−18 .5 kJ
28 g N 2 1 mol N 2 ΔH = −18.5 kJ

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2. Calculate the enthalpy change when 1L (1000 g) of water is evaporated to form water
vapour (gas).
Answer.
1 mol H 2 O +44 . 0 kJ
1000 g H 2 Ox x =+2 . 44 x 10 3 kJ
18 g H 2 O 1 mol H 2 O ΔH = +2.44x103 kJ

Note that it is very important to show the signs and the units throughout, and especially
in the answer, show it as −18.5 kJ as in example 1, and as +2.44x103 kJ in example 2.
Not showing the sign (+ or −), or the correct units will lose you points!!

In the next two sections we will show how we measure heat effects, with a technique
called “calorimetry”, and we will show how we can calculate enthalpy changes for
different reactions using Hess’ law and tables of enthalpy of formation for compounds.

However, after all this theory, let’s summarize what are the important things you should
know at this point.

1. The energy E of a system is the sum of all forms of energy in that system.
2. The first law: energy is conserved, we can convert energy from one form into
another, but no energy can ever be lost or created. The units for energy E, heat q,
and work w all are the joule, J = N.m
3. When we have a chemical reaction or physical change (such as a phase change,
l → g, s→ l, g → l, etc,) the heat effect q is −ve when the process produces
(releases) heat, this is called an exothermic process, and +ve when the process
takes up heat, this is called an endothermic process.
4. The new function enthalpy is defined as H = E + pV, but for a chemical or
physical change at constant pressure (a system open to the atmosphere), this
reduces to ΔH = ΔE + pΔV.
5. Finally, for most systems we will encounter, reactions or processes carried out at
constant pressure, the enthalpy change simply is the heat effect, ΔH =qp . Then,
when we have a chemical or physical process, ΔH = H(producst) − H(reactants).

2. Calorimetry: the measurement of heat effects of chemical reactions

(Chang section 6.5, pp. 239-245)

Heat effects of chemical reactions are measured using a calorimeter. In an adiabatic

calorimeter we completely insulate the instrument from the outside. As a result, any heat
given off by a reaction will be used to heat up the calorimeter and its contents. Let’s say
that we have a reaction
Reactant → Product ΔH = qrxn

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This heat qrxn will be given to the calorimeter and its contents, and as a result qcalorimeter is
+ve:
qcalorimeter = −qrxn = +ve

We have already defined the specific heat s (J/K.g) and the heat capacity C (J/K). In the
case of the calorimeter, C is the heat capacity of the calorimeter, contents and all:

qcalorimeter = CΔT

Where ΔT is the temperature change of the calorimeter and its contents. ΔT is the
measured quantity. We want to find qrxn, and with qrxn = −qcalorimeter we have the calorimetry
equation:
qrxn = −CΔT

This is the basic calorimetry equation you should remember!

Chang describes two types of calorimeters:

a) the constant volume adiabatic calorimeter (also called the “bomb calorimeter”), in
which the system is both isolated and closed (ΔV = 0), therefore qrxn = qV,rxn = ΔU. This
type of calorimeter is used mainly to determine heats of combustion.
b) the constant pressure adiabatic calorimeter. This is the calorimeter you will use in the
Chem 103 laboratory (the “coffee cup calorimeter”), the system is open to the
atmosphere, we measure the heat effect at constant pressure, qp,rxn = ΔH = −CΔT.

For an exothermic reaction, ΔH = qp,rxn = −ve, qcalorimeter = +ve, ΔT is positive, the

temperature of the calorimeter + content increases.
For an endothermic reaction, ΔH = qp,rxn = +ve, qcalorimeter = −ve, ΔT is negative, the
temperature of calorimeter+ contents decreases.

Examples.

1. A 2.00 g sample of cornflakes is combusted in an adiabatic calorimeter. The

calorimeter constant C = 11.7 kJ/K. In the combustion experiment the temperature rises
from 21.22 to 23.93 oC. Calculate the heat of combustion of cornflakes in kJ/g.
Answer.
qcalorimeter = CΔT ΔT = 23.93 − 21.22 = 2.71 oC, but 1oC = 1K, so ΔT = 2.71K.
qcalorimeter = 11.7(kJ/K)x2.71(K) = +31.7 kJ
This is an adiabatic calorimeter, so qcombustion = qrxn = −31.7 kJ This is for 2 g corn flakes,
Therefore: qcombustion = −31.7 kJ/2.00 g = −15.9 kJ/g
Note the signs and the units: qcombustion is −ve, it is an exothermic reaction (the temperature
of the calorimeter increases). For the sample of cornflakes the units of qcombustion are kJ,
when expressed per gram the units are kJ/g. Check this result with the value given (in
very small letters!) on a box of cornflakes; it may be given per 100 g or per “serving’ of a
certain amount).

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2. 1.59 g glucose (C6H12O6) is burned in an adiabatic calorimeter. The calorimeter
constant (calorimeter + contents) is 9.18 kJ/K. In the combustion experiment, the
temperature of the calorimeter rises from 21.30 to 24.18 oC. Calculate the heat of
combustion, qcomb of glucose in a) kJ/g, and b) kJ/mol.
Answer.
Once again the key to this question is in the statement that it is an adiabatic calorimeter.
This means that qcombustion = −qcalorimeter.
qcalorimeter = CΔT ΔT = 24.18 − 21.30 = 2.88 oC = +2.88 K.
qcalorimeter = 9.18(J/K)x2.88(K) = +26.4 kJ → qcombustion = −26.4 kJ
a) This is for the combustion of 1.59 g glucose. Then for 1 g glucose:
qcomb = −26.4 kJ/1.59 g glucose = −16.6 kJ/g
b) The MM of glucose = 180 g/mol.
qcomb = −16.6(kJ/g)x180(g/mol) = −2.99x103 kJ/mol

In general we can write that if for a given we reaction we find a value ΔH for n moles
reacting (in kJ), then the Molar Enthalpy of Reaction ΔHm = ΔH/n (kJ/mol)

3. 25.0 mL 0.500 M H.HCl(aq) is added to 75.0 mL 0.500 M NaOH in an open adiabatic

styrofoam “coffee cup calorimeter”. The temperature rises by 1.68 oC. calculate the
molar enthalpy of neutralization on HCl. The heat capacity of the Styrofoam cup can be
neglected. The heat capacity of 1 mL solution can be assumed to be equal to the heat
capacity of 1 mL (1 g) water.
Answer.
This is a neutralization reaction: HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l).
We have nHCl = 0.500x0.025 = 0.0125 mol, and nNaOH = 0.500x0.075 = 0.0375 mol, so
NaOH is in excess and HCl is the limiting reagent, the HCl is completely neutralized.

First we have to find the calorimeter constant C. We are told that the Styrofoam cup has
no heat capacity itself, therefore it is only the content, (75 + 25 mL = 100 mL solution =
100 g) that represents the heat capacity of the calorimeter.
C = s.m = 4.18(J/K.g)x100(g) = 418 J/K
qcalorimeter = CΔT = 418x1.68 = 702. J → qrxn = −702 J
Since it is an open system, pressure is constant, this is qp,reaction = ΔHrxn
This is ΔHrxn for 0.0125 mol HCl neutralized by excess NaOH.
For the neutralization of 1 mol HCl: ΔHm = ΔH/n = −702 (J) / 0.0125 mol = −5.62x104 J
ΔHm,neutralization = -56.2 kJ/mol

3. Standard enthalpy and Hess’ Law (Chang section 6.6 pp. 246-250)

We wrote earlier that for a reaction:

Reactants → Products ΔHrxn = H(products) − H(reactants).

We now have to define what we mean by the enthalpy of a substance. In these

calculations we use for H the standard enthalpy of formation, ΔHfo of a compound.

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A formation reaction is a reaction (often hypothetical) in which a compound is formed
from its constituent elements under standard conditions (T = 25 oC (298K), p = 1 atm),
and with the elements in the form in which they naturally occur under standard
conditions.

The standard enthalpy of formation of a substance, ΔHfo is the enthalpy change when one
mole of substance is formed in the formation reaction.

Some values of ΔHfo for a number of common compounds are listed in table 6.4 (p. 247),
more extensive tables can be found in Chang Appendix 3, pp. A8-A12.

By its definition, the standard enthalpy of formation of an element in its natural state at
298K, 1 atm pressure (H2(g), O2(g), Fe(s), Cl2(g), C(s), etc.) is zero.

Some examples of formation reactions:

For H2O(l): H2(g) + ½O2(g) → H2O(l) ΔH = ΔHfo(H2O, l) = −285.8 kJ/mol

For SO3(g): S(s) + 1½O2(g) → SO3(g) ΔH = ΔHfo(SO3, g) = −395.2 kJ/mol
For NH3(g): ½N2(g) + 1½H2(g) → NH3(g) ΔH = ΔHfo(NH3, g) = −46.3 kJ/mol
But also:
For H2O(g): H2(g) + ½O2(g) → H2O(g) ΔH = ΔHfo(H2O,g) = −241.8 kJ/mol

Using these values, we can calculate the enthalpy (heat) of reaction of chemical reactions,
but also of phase changes. Note again the importance of always including the phase (s, l,
g), and the signs of the enthalpies.

Examples.
1. Calculate the heat effect (enthalpy change) for the reaction SO2(g) + ½O2 → SO3(g).
Answer.
From Table 6.4 we find the enthalpies of formation: SO2(g) ΔHfo = −296.1 kJ/mol, SO3(g)
ΔHfo = − 395.2 kJ/mol, O2(g) ΔHfo = 0
ΔHrxn = −395.2 −0 −(−296.1) = −99.1 kJ/mol

2. Calculate the heat effect when 2.00 kg CaCO3 is decomposed into CaO(s) and CO2(g).
Answer:
The reaction is: CaCO3(s) → CaO(s) + CO2(g)
Using the ΔHfo values for CaO(s) (−635.6), CO2(g) (−395.5) and CaCO3(s) (−1206.9) all in
kJ/mol, we find:
ΔHrxn = −635.6 +(−395.5) −(−1206.9) = +175.8 kJ/mol
For 2.00 kg (2000 g), n = 2000/100) = 20.0 mol CaCO3:
ΔHrxn = +175.8 (kJ/mol)x 20.0(mol) = +1.35x102 kJ
Note that this decomposition reaction is endothermic, and also once again that you must show the
+ sign in your answer!

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Hess’ Law
Hess’ Law states that when we add, subtract, or multiply reactions, we also add,
subtract, multiply the reaction enthalpy in the same way.

For instance when we have the reactions:

C(s) + ½O2(g) → CO(g) ΔH = −110.5 kJ/mol
and CO(g) + ½O2(g) → CO2(g) ΔH = −283.0 kJ/mol +
we can add the two reactions, then we can also add the enthalpies
C(s) + O2(g) → CO2(g) ΔH = −393.5 kJ/mol

Or, when we have the reaction:

H2O(l) → H2O(g) ΔH = + 44.0 kJ/mol,
Then for the reaction:
H2O(g) → H2O(l) ΔH = −44.0 kJ/mol

Examples.
1. Calculate the enthalpy change for the combustion of 100 g natural gas, (methane, CH4)
under standard conditions using the enthalpy of formation data in Appendix 3.
Answer.
As always, we first balance the combustion reaction:
CH4(g) + 3O2(g) → CO2(g) + 2H2O(l)

ΔHfo −74.9 0 −393.5 −285.8 kJ/mol

ΔHcombustion = −393.5 +2x(−285.8) −(−74.9) = −890.2 kJ/mol

For 100 g = 100/16.0 = 6.25 mol:
ΔHcombustion = −890.2 (kJ/mol)x6.25 (mol) = −5.56x103 kJ

2. The ΔHcombustion for benzene(l), C6H6(l) , under standard conditions is –3.218x103 kJ/mol.
Using only the values for ΔHfo for CO2(g) and H2O(l) from Table 6.4, find the standard
enthalpy of formation of benzene(l).
Answer.
The combustion reaction is:
C6H6(l) + 7½O2(g) → 6CO2(g) + 3H2O(l) ΔHcombustion = −3.267x103 kJ/mol

−3.267x103 kJ/mol = 6x(−393.5) + 3x(−285.8) − ΔHfo(C6H6, l)

→ −ΔHfo(C6H6, l) = −3.267x103 −(−3.218x103) = +49.0 kJ/mol
ΔHfo(C6H6, l) = + 49.0 kJ/mol

3. We know the enthalpy changes for the following reactions:

SO2(g) + H2O(l) → H2SO3(aq) (1) ΔH1 = −42 kJ/mol
SO3(g) + H2O(l) → H2SO4(aq) (2) ΔH2 = −227 kJ/mol
SO2(g) + ½O2(g) → SO3(g) (3) ΔH3 = −99 kJ/mol
Using these data only, use Hess’ law by combining equations 1, 2 and 3 in such a way
that you can calculate the enthalpy change (heat effect) for the reaction:
H2SO3(aq) + ½O2(g) → H2SO4(aq)

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Answer.
We have to combine reactions (1), (2), and (3) in such a way that they add up to the
reaction we want. We can see that we want H2SO4 on the “right hand side”, but H2SO3 on
the “left hand side”, therefore we reverse reaction (1):
H2SO3(aq) → SO2(g) + H2O(l) (−1) ΔH−1 = +42 kJ/mol
Now we can add reactions (3) and (2):
SO2(g) + ½O2(g) → SO3(g) (3) ΔH3 = −99 kJ/mol
SO3(g) + H2O(l) → H2SO4(aq) (2) ΔH2 = −227 kJ/mol +
H2SO3(aq) + ½O2(g) → H2SO4(aq) ΔH = +42 +(−99) +(−227) = −284 kJ/mol

Exercises (use ΔHfo values from Table 6.4 or Appendix 3 as needed).

1. Calculate the energy needed to heat 51.5 g Fe (s = 0.444 J/(K.g)) from 25 oC to 700 oC.

2. For the reaction: MgCO3(s) → MgO(s) + CO2(g), qp = ΔH = +117 kJ/mol

Calculate the heat effect when 100 g MgCO3 decomposes into MgO and CO2.

3. Calculate the heat effect when 180 g water is evaporated under standard conditions.

4. The heat effect of the reaction Zn(s) + ½O2 → ZnO(s) is determined in a calorimeter
with a calorimeter constant C = 5.60x103 J/K. When 1.24 g Zn reacts with oxygen, the
temperature of the calorimeter and contents rises from 22.24 to 23.42 oC. Calculate the
heat effect of the reaction in kJ/(mol Zn).

5. The heat effect of the neutralization reaction NaOH(aq) + HCl(aq) is measured in an

open adiabatic solution calorimeter (not a coffee cup calorimeter) The heat capacity of
the calorimeter itself is 456 J/K. The heat capacity of the solution may be assumed to be
equal to that of water, 4.18 J.g). When 40 mL 0.600 M NaOH(aq) is added to 100 mL 1.0
M HCl(aq) the temperature rises 1.29 oC. Calculate the molar enthalpy of neutralization,
ΔHm,neutralization(kJ/mol NaOH).

6. Using the values for the standard heat of formation in Appendix 3, calculate the
standard enthalpy of combustion of ethanol, C2H6O(l). First balance the combustion
reaction!

7. The heat of combustion of glucose (C6H12O6(s)) is −2.80x103 kJ/mol. Calculate the

standard enthalpy of formation of glucose(s), ΔHfo(glucose).

Answers. 1. q = +15.4 kJ; 2. qp = +139 kJ; 3. qp = +440 kJ; 4. qrxn = −348 kJ/mol;
5.ΔHneutralization= −56.2 kJ/mol; 6. ΔHcombustion =−1.367 kJ/mol ; 7. ΔHfo = −1.28x103 kJ/mol.

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