Thermochemistry

Energy
The capacity to do work or to transfer
heat.
Work:
Energy used to cause an object that has mass
to move.

Heat:
Energy used to cause the temperature of an
object to rise.

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 Potential Energy
Energy an object possesses by virtue of its position or
chemical composition.
Potential energy and
kinetic energy. The
potential energy initially
stored in the motionless
bicycle at the top of the
hill is converted to kinetic
energy as the bicycle
moves down the hill and High potential Decreasing
loses potential energy. energy, zero potential energy,
kinetic (a)
energy increasing kinetic
(b)
energy

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Kinetic Energy

Energy an object possesses by virtue of its

motion:

1
= 2
2

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 Units of Energy
The SI unit of energy is the joule (J).

=

An older, non-SI unit is still in widespread use: The calorie
(cal).
1 cal = 4.184 J
Note: Energy unit used in nutrition is the Calorie (note the capital C):
1 Cal = 1000 cal = 1 kcal

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System and Surroundings

The system includes the

molecules we want to study
(here, the hydrogen and
oxygen molecules).
The surroundings are
everything else (here, the
cylinder and piston).

2 H2 + O2 2 H2O + Energy

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Work

Energy used to move an object over some

distance:
w=Fxd

where w is work, F is the force, and d is the

distance over which the force is exerted.

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Heat

Energy can also be transferred as heat.

Heat flows from warmer objects to cooler

objects.

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First Law of Thermodynamics

Energy is neither created nor destroyed; it is

conserved.

In other words, the total energy of the universe

is a constant; if the system loses energy, it must
be gained by the surroundings, and vice versa.

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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 (U-used in some
textbooks).

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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 Internal Energy
Energy gained from Red arrow pointing
surroundings, E of up from initial state = Final state
system increases, gain of energy by the of the system
system Efinal
E positive
Initial state
Einitial Efinal
of the system

Blue arrow pointing

down from initial Final state
Efinal
state = loss of Energy lost to
of the system
energy from the surroundings, E of
system system decreases, E
negative

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 Changes in Internal Energy
When energy is exchanged
System
between the system and the
Heat q>0 surroundings, it is exchanged
as either heat (q) or work (w).
Surroundings
That is: E = q + w.
Work w>0
E > 0

For q + means system gains heat means system loses heat

For w + means work done on system means work done by system
For E + means net gain of energy by system means net loss of energy by system

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 Changes in Internal Energy

If E > 0
H2(g), O2(g)
i.e. Efinal > Einitial

Therefore, the system

E < 0 E > 0 absorbed energy from the
Internal energy, E

surroundings.
This energy change is
called endothermic.

H2O(l)

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 Changes in Internal Energy

If E < 0
H2(g), O2(g)
i.e. Efinal < Einitial

Therefore, the system

E < 0 E > 0 released energy to the
Internal energy, E

surroundings.
This energy change is called
exothermic.

H2O(l)

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State Functions

Usually we have no way of knowing the

internal energy of a system; finding that
value is simply too complex a problem.

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 State Functions
However, we do know that the internal energy of a system is
independent of the path by which the system achieved that
state.

In the system below, the water could have reached room

temperature from either direction.

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State Functions

Therefore, internal energy is a state function.

It depends only on the present state of the system,

not on the path by which the system arrived at that
state.

And so, E depends only on Einitial and Efinal.

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State Functions
However, q and w are
not state functions.
Whether the battery is
shorted out or is
discharged by running
the fan, its E is the
same, but q and w are
different in the two
cases.

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Enthalpy
If a process takes place at constant pressure (as do
the majority of processes we study) and the only work
done is this pressure-volume work, we can account for
heat flow during the process by measuring the
enthalpy of the system.
Enthalpy is the internal energy plus the product of
pressure and volume:

H = E + PV

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Enthalpy

When the system changes at constant

pressure, the change in enthalpy, H, is

H = (E + PV)
or
H = E + PV

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Enthalpy
Since E = q + w and w = PV, we can
substitute these into the enthalpy expression:
H = E + PV
H = (q + w) w
H = q

So, at constant pressure, the change in

enthalpy is the heat gained or lost.

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 Enthalpies of Reaction

The change in enthalpy, H, is the enthalpy of the products

minus the enthalpy of the reactants and is called the enthalpy
of reaction or the heat of reaction.
H = Hproducts Hreactants
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 About Enthalpy
1. Enthalpy is an extensive property.
1 mol CH4 ~ -890 kJ, and 2 mol ~ 1780 kJ!!

2. H for a reaction in the forward direction is equal in

size, but opposite in sign, to H for the reverse
reaction.

3. H for a reaction depends on the state of the

products and the state of the reactants.
E, P & V are state functions

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Calorimetry

Since we cannot know the exact enthalpy of

the reactants and products, we can measure
H through calorimetry, the measurement of
heat flow.

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Heat Capacity and Specific Heat

The amount of energy required to raise the

temperature of a substance by 1 K (1C) is its heat
capacity.

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 and Specific Heat

(quantity of heat transferred)

Specific heat capacity =
(grams of substance) (temperature change)

or
q
C= m T

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Constant-Pressure Calorimetry
By carrying out a reaction in
aqueous solution in a simple
calorimeter such as this one, one
can indirectly measure the heat
change for the system by
measuring the heat change for
the water in the calorimeter.

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Constant-Pressure Calorimetry
Because the specific heat for water is
well known (4.184 J/g K), we can
measure H for the reaction with this
equation:
qsoln = -qrxn

qsoln = (specific heat of solution) x (grams of solution) T = qrxn

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Bomb Calorimetry (Constant-Volume Calorimetry
Reactions can be carried
out in a sealed bomb,
such as this one, and
measure the heat
absorbed by the water.

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Bomb Calorimetry (Constant-Volume Calorimetry)

Because the volume in the bomb calorimeter

is constant, what is measured is really the
change in internal energy, E, not H.

For most reactions, the difference is very

small.

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 Calorimetry example

How much heat is given off when an 869 g iron bar

cools from 94 C to 5 C?

(specific heat of Fe = 0.444 J g-1 K-1)

Ans= -34,000 J

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Example
In a neutralization reaction between a strong acid and
a strong base, the following reaction forms water.

H+(aq) + OH-(aq) H2O(l)

If 25.00 mL of 2.50 M HCl and 25.00 mL of 2.50 M

NaOH, both at 21.1 C react and the final
temperature is 37.8 C, determine the heat of the
neutralization reaction expressed per mole of H2O
formed.
specific heat for water ~ (4.184 J/ g K)

Ans = - 56 kJ/mol H20

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Hesss Law

H is well known for many reactions, and it

is inconvenient to measure H for every
reaction in which we are interested.

However, we can estimate H using H

values that are published and the properties
of enthalpy.

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Hesss Law
Hesss law states that If a
reaction is carried out in a
series of steps, H for the
overall reaction will be
equal to the sum of the
enthalpy changes for the
individual steps, or simply:

H1 = H2 + H3

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 Enthalpies of Formation
Enthalpy of formation, , is defined as the enthalpy
change for a reaction in which a compound is made from
its constituent elements, and all reactants and products are
in their standard states.

Other enthalpies are extensively tabulated, E.g.

enthalpies of vaporization ( for converting liquids to gases),
enthalpies of fusion ( for melting solids),
enthalpies of combustion ( for combusting a substance in oxygen), and so forth

Important!
Can calculate enthalpy changes for a great many reactions from
tabulated values

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Standard Enthalpies of Formation
Standard enthalpies of formation, , are measured under
standard conditions (298 K and 1.00 bar pressure).
Substance Formula (kJ/mol) Substance Formula (kJ/mol)
Acetylene C2H2(g) 226.7 Hydrogen chloride HCl(g) -92.3
Ammonia NH3(g) -46.19 Hydrogen fluoride HF(g) -268.6
Benzene C6H6(l) 49 Hydrogen iodide HI(g) 25.9
Calcium carbonate CaCO3(s) 1207.1 Methane CH4(g) -74.8
Calcium oxide CaO(s) -635.5 Methanol CH3OH(l) -238.6
Carbon dioxide CO2(g) -393.5 Propane C3H8(g) -103.85
Carbon monoxide CO(g) -110.5 Silver chloride AgCl(s) -127
Diamond C(s) 1.88 Sodium bicarbonate NaHCO3(s) -947.7
Ethane C2H6(g) -84.68 Sodium carbonate Na2CO3(s) -1130.9
Ethanol C2H5OH(l) -277.7 Sodium chloride NaCl(s) -410.9
Ethylene C2H4(g) 52.3 Sucrose C12H22O11(s) -2221
Glucose C6H12O6(s) -1273 Water H2O(l) -285.8
Hydrogen bromide HBr(g) -36.23 Water vapour H2O(g) -241.8

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Calculation of H

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

Imagine this as occurring in 3 steps and the sum of these

three equations is:

C3H8 (g) 3 C (graphite) + 4 H2 (g) Equation 1

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Calculation of H

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

Imagine this as occurring in 3 steps and the sum of

these three equations is:

Equation 1
C3H8 (g) 3 C (graphite) + 4 H2 (g)
3 C (graphite) + 3 O2 (g) 3 CO2 (g) Equation 2

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 Calculation of H
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

Imagine this as occurring in 3 steps and the sum of these

three equations is:

C3H8 (g) 3 C (graphite) + 4 H2 (g) Equation 1

3 C (graphite) + 3 O2 (g) 3 CO2 (g) Equation 2
4 H2 (g) + 2 O2 (g) 4 H2O (l) Equation 3

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Calculation of H
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

Imagine this as occurring in 3 steps and the sum of these

three equations is:

C3H8 (g) 3 C (graphite) + 4 H2 (g) Equation 1

3 C (graphite) + 3 O2 (g) 3 CO2 (g) Equation 2

4 H2 (g) + 2 O2 (g) 4 H2O (l) Equation 3

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

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Calculation of H

We can use Hesss law in this way:

H = nHf(products) - mHf(reactants)

where n and m are the stoichiometric

coefficients.

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Calculation of
H

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

H =nf H(products) - mf H(reactants)
H = [3(-393.5kJ) + 4(-285.8kJ)] - [1(-103.85kJ) + 5(0kJ)]
= -2220 kJ
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 Example:
Calculate the standard enthalpy of
formation of CS2 (l) given that:
C(graphite) + O2 (g) CO2 (g) H0 = -393.5 kJ
S(rhombic) + O2 (g) SO2 (g) H0 = -296.1 kJ
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) H0 = -1072 kJ

H0 = 86.3 kJ

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