CEM1008F

Thermochemistry and the 1st law of

Thermodynamics

Silberberg chapter 6 1
 Thermochemistry
Study of the quantity of heat absorbed or evolved in a chemical reaction

System = what we are studying e.g. reaction or physical change

Surroundings = everything else
Heat is defined as the energy that flows into or out of a system because of
a difference in temperature between the system and its surroundings.

For example: 2 H2 + O2  2 H2O + energy

The system includes the molecules

we want to study; in this case the
hydrogen and oxygen molecules.

The surroundings are everything

else; the cylinder and piston.

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 Three Types of Systems

isolation
Open System Closed System
Can gain or lose Absorb and release Isolated System
mass and energy, but not Cannot exchange
energy across mass, across the energy or mass, energy
the boundary boundary is constant!
 Thermodynamics
This the science of energy and its transformations. Thermochemistry
deals with heat in chemical and physical change.
• Heat energy is associated with molecular motions.
• Heat is transferred until thermal equilibrium is established.

First Law of Thermodynamics

• Energy is neither created nor destroyed; it is conserved.
• Thus the total energy of the universe is a constant. If the system loses
energy, the energy must be gained by the surroundings and vice versa.
All of thermodynamics depends on the law of CONSERVATION OF
ENERGY i.e. the total energy is unchanged in a chemical reaction.
Internal Energy
The internal energy of a system is the sum of all kinetic and potential
energies of all components of the system; we call it E.
By definition, the change in internal energy, E, is the final energy of
the system minus the initial energy of the system: E = Efinal − Einitial
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 Energy changes in chemical reactions

ENERGY is the capacity to do work or transfer heat.

HEAT is the transfer of thermal energy between two bodies that

are at different temperatures.
Temperature is a measure of the thermal energy.
Temperature  Thermal Energy

Units of Energy
kg m2
The SI unit of energy is the Joule 1 J = 1  = 1 kg m2 s-2
s2

The calorie, an older, non-SI unit is still in widespread use

• The calorie (cal) 1 cal = 4.184 J
• 1000 cal = 1 kcal = 1 Calorie (a “food” calorie)
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 Work (w) and Heat (q)
• Work
– This is the energy used to move an object against an opposing
force (a system does work when it expands against pressure.
This is called PV-work, where w = -PV)
– e.g. in a car engine, fuel (hydrocarbon)  O2 ( g ) 
 CO2 ( g )  H 2O( g )

– We use the symbol w

• Heat:
– This is the energy used to increase the temperature of an object
– Heat is transferred from the hot to the colder object
– We will use the symbol q
• Heat and work can be considered as energy in transit
• The total change in energy is the sum of work done and heat
transferred
 The Sign Convention

• The sign conventions for work and heat transfer are very important
• Heat transferred to the system or work done on the system, is
positive (incoming)
• Heat transferred from the system, or work done by the system
on the surroundings, is negative (outgoing)

q + w = E
+ + +
+ - Depends
- + Depends
- - -
 Changes in Internal Energy
When energy is exchanged between the system and the
surroundings, it is exchanged as either heat (q) or work (w).

E = q + w
A system transferring energy as heat only i.e. w = 0, see S&A 6.3 below.

S&A 6.3

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Changes in Internal Energy – Exothermic reactions

S&A 6.2A If E < 0

i.e. Efinal < Einitial

Therefore, the system released

energy to the surroundings.
This energy change is called
exothermic e.g. combustion of
methane, CH4.

Heat always transfers from a hotter Tsystem goes down; system

object to cooler one. loses energy
EXOthermic: heat transfers from Tsurr goes up; surroundings
SYSTEM to SURROUNDINGS. gain energy

Note the direction of the arrow showing E.

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Changes in Internal Energy – Endothermic reactions

S&A 6.2B If E > 0

i.e. Efinal > Einitial

Therefore, the system absorbed

energy from the surroundings.
This energy change is called
endothermic e.g. melting of ice.

Heat always transfers from a hotter Tsystem goes up; system

object to cooler one. absorbs energy
ENDOthermic: heat transfers from Tsurr goes down;
SURROUNDINGS to SYSTEM. surroundings lose energy

Look at direction of heat flow for reactions or processes. 10

 Work Done by an Expanding Gas

Total change in internal energy:

Pressure
External
E  q  w
Pressure
External

P
Total change in internal
energy, keeping the Total change in
P volume fixed:
V internal energy,
allowing PV
E  qV  0 work:
qV  qV  E qP E  qP   PV 
 qP  E  PV
PV-work done by PV-work done by
gas on w  PV 0 gas on w   PV
surroundings: surroundings:
 Introducing Enthalpy
• Internal energy changes (and heat transfer), which may include
PV-work, will be different under conditions of constant volume and
constant pressure
• In lab conditions, constant pressure is normally preferred (e.g.
experiments done in open systems at atmospheric pressure)
• We thus define a new quantity, called the enthalpy,

H  E  PV

• This gives the heat transfer (which we can measure for chemical
reactions) under constant pressure conditions, and negates the
need to determine PV work as well!
 Enthalpy
Most chemical reactions occur at constant pressure, P.
Heat transferred at constant pressure, P, is equal to qp, thus
qp = H, where H = enthalpy
Recall: E = q + w; thus E = H + w
and since w is usually small
H  E This is the heat transferred at constant P is
approximately equal to the change in internal energy
H = change in heat content of the system
H = H final – H initial
1. Enthalpy is an extensive property, it depends on amount of substance.
2. Enthalpy is a state function i.e. it depends only on the present state of
the system, not on the path by which the system arrived at that state.

3. H for a reaction in the forward direction is equal in size, but opposite in

sign, to H for the reverse reaction.
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 Interpreting the Enthalpy
• The enthalpy, H  E  PV , is equal to the energy change for
the following reactions:
– Reactions that do not involve gases (liquids and solids have small
volume changes)
2 KOH (aq) + H2SO4 (aq) K2SO4 (aq) + 2 H2O (l)
– Reactions in which the moles of gas does not change
N2 (g) + O2 (g) 2 NO (g)
– Reactions in which qp >>> PV

H2 (g) + ½ O2 (g) H2O (g)

H  483.6 kJ PV  2.5 kJ

E  H  PV   483.6 kJ    2.5 kJ   481.1 kJ
 Special Types of Enthalpy Changes
• Heat of combustion:
– 1 mol of a compound reacts with O2 in a combustion
C4H10 (l) + 13/2 O2 (g) 4 CO2 (g) + 5 H2O (g)
• Heat of formation:
– 1 mol of a compound is produced from its elements
K (s) + ½ Br2 (l) KBr (s)

• Heat of vapourisation:
– 1 mol of a substance vapourizes
C6H6 (l) C6H6 (g)
• Heat of fusion:
– 1 mol of a substance melts
NaCl (s) NaCl (l)
 Enthalpy of reactions
H = H (products) – H (reactants)
Enthalpy diagrams for exo- and endothermic processes

Combustion of methane Melting of ice

CH4 + 2 O2  CO2 + 2 H2O H2O (s)  H2O (l)

S6.8
Hproducts < Hreactants Hproducts > Hreactants
H < 0 H > 0
Exothermic Endothermic 16
 Thermochemical equations
A thermochemical equation is a chemical equation for a reaction which
includes the states of matter and the heat of reaction, Hrxn.

The value of Hrxn refers to the amounts (moles) of substances and

their states of matter in that specific equation e.g. in the reaction
below 2 mol, 45.98 g, of Na reacts with water. Note Na = 22.99 g mol-1.

2 Na (s) + 2 H2O (l)  2 NaOH (aq) + H2 (g); H = -367.5 kJ

The phase labels are important because H depends on the phase of the
substances.

The quantity of heat obtained for a reaction will depend on the amount of
reactants.
Apply the strategies used to solve stoichiometry problems to those
involving enthalpy.
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 Two important rules for working with thermochemical equations:

(i) Enthalpy is an extensive property i.e. depends on mass.

When a thermochemical equation is multiplied by any factor,
the value of H for the new equation is obtained by multiplying
the original H by the same factor.

N2 (g) + 3 H2 (g)  2 NH3 (g); H = -91.8 kJ (1)

(1) x 2 2 N2 (g) + 6 H2 (g)  4 NH3 (g); H = -91.8 x 2 kJ

= -183.6 kJ

(ii) When a chemical equation is reversed, the value of H is

reversed in sign.
2 NH3 (g)  N2 (g) + 3 H2 (g) ; H = -91.8 kJ x -1

= + 91.8 kJ
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 Calculation using a thermochemical equation
Calcium oxide reacts with water to produce calcium hydroxide:

CaO (s) + H2O (l)  Ca(OH)2 (s); H = -65.2 kJ

How much heat will be gained if 28.4 g of calcium oxide reacts?

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 Calorimetry: measuring heats of reaction

Since we do not know the exact enthalpy of the reactants and

products, we can measure H through calorimetry, the
measurement of heat flow.
q  T

Heat Capacity and Specific Heat - Definitions

Heat capacity is the amount of energy required to raise the
temperature of a substance by 1 K (1C).

We define specific heat capacity (or simply specific heat) as the

amount of energy required to raise the temperature of 1 g of a
substance by 1 K.

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 Heat capacity
Thermochemical measurements are based on the relationship between
heat and temperature change.

When a substance is heated, the quantity of heat absorbed, q, is

proportional to the change in temperature thus:
q
q  T or q = constant x T or = constant
T

Thus the heat capacity of a substance is the quantity of heat needed to

raise the temperature of a sample of a substance one degree celcius or
Kelvin.
q
Heat capacity =
T

Where T = Tfinal – Tinitial

Remember a change of 1C is the same as a change of 1 K.

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 Specific heat capacity
Heat capacity is proportional to the amount of substance. The specific
heat capacity is the quantity of heat required to change the temperature of
1 g of substance by 1C or 1K.

q = c x m x T

where T = Tfinal – Tinitial m is the mass of a substance

c is the specific heat capacity of that substance.
The molar heat capacity of a substance is the heat capacity for 1 mole of
that substance.

Calorimetry: Laboratory measurement of heat of reaction

The calorimeter is a device used to measure the heat released or
absorbed by a chemical or physical process.
Heat is transferred from a system to the surroundings and vice versa.
The calorimeter is the “surroundings” that we use to measure the
temperature change that results from the heat transfer.
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 c (J g-1 K-1)*

Specific heat
capacities of
selected
substances

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 The “coffee-cup” calorimeter

The coffee-cup calorimeter is a

constant pressure calorimeter.

Since the temperature change

occurs at constant pressure, the
heat transferred can be related
directly to the enthalpy change,
H. We use the relationship:

̶ q sample = +q H2O

For example q = c x m x T S&A 6.9

qrxn = (specific heat of sample) x (grams of sample) x T
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 Constant Volume Calorimetry

• A bomb calorimeter is used to electrical leads thermometer

determine constant volume to ignite sample
+ -
heat transfer, qV, for a reaction stirrer
• Most often used for
combustion reactions
• Due to complexity of the
surroundings, the heat capacity
of the entire calorimeter (Ccal) is
needed sample
cup
qrxn = -Ccal x T
• Note, at constant volume, oxygen

qrxn  qV  E bomb reaction Water

chamber
 Examples based on specific heat and specific heat capacity
Sample problem 6.4
Finding the quantity of heat from a temperature change.
A layer of copper welded to the bottom of a skillet (frying pan) has a mass of
125 g. How much heat is needed to raise the temperature of the copper
layer from 25C to 300C?
The specific heat capacity for copper is 0.387 J g-1 K-1.

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Sample problem 6.5: Determining the specific heat capacity of a solid
You heat 22.05 g of a solid in a test tube to 100.00C and add it to 50.00 g of
water in a coffee-cup calorimeter. The temperature of the water changes from
25.10C to 28.49C. The specific heat capacity of water is 4.184 J g-1 K-1. Use
this data to determine the specific heat capacity of the solid.

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 Hess’s Law of Heat Summation
One of the most useful applications of the state-function of enthalpy, H, is that
it allows us to find out H for any reaction or process even if we cannot carry
out the reaction easily in a laboratory or it occurs in more than one step.

Hess’s law states that the enthalpy change of an overall process is the
sum of the enthalpy changes of the individual steps.
Consider the reaction:
2 Cgraphite + O2 (g)  2 CO (g) [Target reaction]
You cannot determine the enthalpy change directly. The CO that forms
reacts with the oxygen present in the reaction mixture to form CO2.

Use Hess’s law to combine the two reactions below to obtain H for the
target reaction:
2 Cgraphite + 2 O2 (g)  2 CO2 (g); step 1
2 CO2 (g)  2 CO (g) + O2 (g); step 2

2 Cgraphite + O2 (g)  2 CO (g) Target reaction

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The enthalpy change for step 1 can be obtained by burning graphite in pure oxygen
Cgraphite + O2 (g)  CO2 (g); H = -393.5 kJ (a)
You cannot carry out the second step on slide 28 but the reverse of step 2 is possible
as CO can be reacted with pure oxygen;
2 CO + O2  2 CO2, H = -566.0 kJ (b)
Apply Hess’s Law and the guidelines for thermochemical reactions on slide 13&18.
2 x (a) 2 C graphite + 2 O2 (g)  2 CO2 (g); H = 2 x (-393.5) kJ 
-1 x (b) 2 CO2 (g)  2 CO (g) + O2 (g); H = -1 x (-566.0) kJ 

 2 C graphite + O2 (g)  2 CO (g); H = -221.0 kJ  Target reaction

Enthalpy diagram
illustrating Hess’s Law

+ =

E&G 10 edition 6.17

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Campsite analogy for state functions and Hess’s Law

The difference in
altitude between two
camps is 3600 feet
and does not
depend on the path
taken. This is
similar to a state
function.

E&G 10 edition 6.8 30

Standard enthalpies of formation; standard heats of reaction
Apply Hess’s law to determine the enthalpy changes for reactions.

Thermodynamic variables such as enthalpies vary with the conditions. To compare

heats of reaction, chemists have established standard states, i.e. specified
conditions.

When H has been measured with all substances in their standard states it is
written as H o.

H of is applied to a value of H o only when 1 mole of the substance is formed

from its elements in their standard states. H of is measured in kJ mol-1.

The standard state for solutions is 1 mol dm -3.

In general for a reaction Hrxn can be obtained from

Horxn =  m Hof (products) -  n Hof (reactants)

where  equals the sum of H of values and m and n are the co-efficients of the
substances in the chemical reaction.

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 Hof (kJ mol-1)

Selected
Standard
Enthalpies of
Formation at
298 K

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 Using standard enthalpies of formation

In most cases you would consult Appendix B in Silberberg and Amateis

and use the values to determine the enthalpy of formation for a particular
reaction, see Silberberg & Amateis, sample problem 6.11 (8th edition) on
the next slide.
Procedure when Hf for a compound is not available:

Assume that you are asked to carry out a calculation of Horxn involving
a compound such as NaOH (aq). You consult Appendix B and can only
find the value of Hof for NaOH (s).

You remember that NaOH (aq) contains the ions, Na+ (aq) and OH- (aq).
Hof is listed for these ions.

Hof NaOH (aq) = Hof Na+ (aq) + Hof OH- (aq)

= -239.7 kJ mol-1 + (-229.9) kJ mol-1
= -469.9 kJ mol-1
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Sample Problem 6.11

in Table 6.3.

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General process for determining H rxn from values of H f

S6.12

Horxn can be considered as the sum of enthalpy changes for the two step process:

1 decomposition of reactants to their elements, - n Hof (reactants)

2 formation of products from their elements,  m Hof (products)

m and n are the amounts (moles) of the products and reactants and are
equal to the co-efficients in the balanced equation. 35
Applications of thermochemistry: heat and cold packs
Sodium acetate heat packs - The following slightly edited
explanation of how these heat packs work is taken from
http://home.howstuffworks.com/question290.htm
These heat pads are extremely cool to watch. Bending the metal disk starts the
crystallization process, and you can see the crystallization proceed through the
liquid.
What is happening here is strange, but the process can be understood if you think
about water freezing. Water freezes at 0C. If you were to place a thermometer
into a cup of water and put the cup in the freezer, you would find that the
temperature of the water falls to 0C and then stays constant until all the water is
completely frozen. Then the temperature of the solid water falls to the temperature
of the freezer. The process of freezing is exothermic which is hard to understand
until you realise that the opposite process, melting, requires heat to occur and is
thus endothermic.
What if you could somehow supercool the water? That is, say that you could get
the temperature of water to 10 degrees below the freezing point without it
crystallizing into a solid, if you tap the glass the temperature of the water will rise to
0C and the water will solidify quickly. 36
A heat pack like the one available from local pharmacies contains sodium acetate
and water. It turns out that sodium acetate is very good at supercooling. It freezes
at 54C, but it can exist as a liquid at a much lower temperature and is extremely
stable.
Clicking the disk, however, has the ability to force a few molecules to move to the
solid state, and the rest of the liquid then starts to solidify as well. The temperature
of the solidifying liquid rises to 54C in the process.

Watch this process at https://home.howstuffworks.com/mpeg/q290.mpg

Ammonium chloride cold packs

There are chemical reactions you can do to make things cold. Reactions that
absorb heat from the environment are called endothermic reactions. A common
example is a chemical ice pack, which usually contains water and a packet of
ammonium chloride. The cold pack is activated by breaking the barrier separating
the water and ammonium chloride, allowing them to mix.

http://chemistry.about.com/b/2006/03/22/cold-packs-endothermic-reactions.htm

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