Melc 124 127 Thermochemistry

Thermochemistry
General Chemistry 2
1
Learning Competencies
 Explain the First Law of Thermodynamics
(STEM-GC11TC-IIIg-i-124)
Explain enthalpy of a reaction
Calculate the change in enthalpy of a given
reaction using Hess Law
2
Physical and Chemical changes are
accompanied by energy change
 Burning of fuels releases energy
 Boiling of water or cooking of food require
energy
3
Physical and Chemical changes are
accompanied by energy change
 Photosynthesis need energy from the sun
in order to happen
4
Chemical Reaction
1. Exothermic - energy is released to the
surroundings when a change occurs.
Condensation – gas to liquid
(release to form the bonds)
5
Chemical Reaction
2. Endothermic – energy is absorbed from the
surroundings when a change occurs.
Boiling – liquid to gas
(absorb to break the bonds)
6
Interconversion of energy from one
form to another
1. Chemical to Electrical energy in batteries
7
Interconversion of energy from one
form to another
2. Water in a dam being converted to Electrical
energy – hydroelectric power
8
Thermochemistry
study of heat and energy changes that
accompany physical and chemical processes
Chem 11 | General Chemistry II 9

The First Law of Thermodynamics
• Law of conservation of energy - energy can
neither be created nor destroyed. In short
energy is conserved.
• Energy may be transformed from one form to
another and that any energy lost by the
system must be gained by the surroundings,
and vice versa.
• The energy contained within the system,
referred to as internal energy, E.
Internal Energy
• We define the internal
energy, E, of a system as
the sum of all the
kinetic and potential
energies of the
components of the
system.
• In chemical reaction,
𝟐𝑯𝟐 𝒈 + 𝑶𝟐 𝒈 → 𝟐𝑯𝟐 𝑶 𝒍
Internal Energy
• In chemical reaction,
the initial state of the
system refers to the
reactants and the final
state refers to the
products.
𝟐𝑯𝟐 𝒈 + 𝑶𝟐 𝒈 → 𝟐𝑯𝟐 𝑶 𝒍
Relating ∆𝐸 to the Heat and Work
A system may exchange energy with its surroundings
in two ways: as heat or as work. The internal energy
of a system changes in magnitude as heat is added
to or removed from the system or as work done on
or by the system.
Relating ∆𝐸 to the Heat and Work
• When a system undergoes any chemical or
physical change, the accompanying change in
internal energy, ∆𝐸, is the sum of the heat
added to or liberated from the system, q, and
the work done on or by the system, w.
∆𝐸 = 𝑞 + 𝑤
Sample Problem 1
Gases A(g) and B(g) are confined in a cylinder-and-piston
arrangement and react to form a solid product C(s): A(g) +
B(g)→ C(s). As the reaction occurs, the system loses 1150 J of
heat to the surroundings. The piston moves downward as the
gases react to form a solid. As the volume of the gas decreases
under the constant pressure of the atmosphere, the
surroundings do 480 J of work on the system. What is the
change in the internal energy of the system?
Solution: ∆𝐸 = 𝑞 + 𝑤
= − 1150 𝐽 + 480 𝐽
= − 670 𝐽
670 Joules (J) of energy has been transferred from the system
to the surroundings
Sample Problem 2
Calculate ∆𝐸 if 100 kJ of heat energy is absorbed by
the system and 30 kJ of work is done on the
surroundings.
Answer: 70kJ
Sample Problem 3
Calculate the change in the internal energy for a
process in which a system absorbs 140 J of heat from
the surroundings and does 85 J of work on the
surroundings.
Enthalpy of a Chemical Reaction –
Thermochemical Equations
• Most chemical reactions in laboratories and even in

living systems occur under constant pressure.
• During such chemical reactions carried out in vessels
exposed to atmospheric pressure, energy change
between the system and the surroundings usually
involve heat transfer only.
• The amount of work involved under this condition is
very minimal.
• Since the work involved is negligible, the energy
exchanged is usually in the form of heat.
Enthalpy of a Chemical Reaction
• The term enthalpy, from the Greek word,

enthalpien, meaning “to warm” refers to the
energy transferred under constant pressure. It is
represented by the symbol, H. It is often referred to,
as heat content.
• Enthalpy cannot be measured, but, it is possible to
measure the change in enthalpy or heat content,
∆𝑯.
Enthalpy of a Chemical Reaction
The sign of ∆𝐻 indicates the direction of heat transfer.
A positive value of ∆𝐻, indicates that the system
absorbs heat from the surroundings and is, therefore,
endothermic. A negative value indicates that heat is
released by the system, hence, the process is
exothermic.
Endothermic: 𝒒 = ∆𝑯 > 𝟎 ; 𝑯𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 > 𝑯𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
Exothermic: 𝒒 = ∆𝑯 < 𝟎 ; 𝑯𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 < 𝑯𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
Determining the sign of ∆𝑯
• Indicate the sign of enthalpy change, ∆𝐻, in these
process carried out under atmospheric pressure and
indicate whether each process is endothermic or
exothermic:
1. An ice cube melts
Ans. ∆𝐻 is positive and is Endothermic
2. 1 g of butane (𝐶4 𝐻10 ) is combusted in sufficient
oxygen to give complete combustion to
𝐶𝑂2 𝑎𝑛𝑑 𝐻2 𝑂.
Ans. ∆𝐻 is negative and is Exothermic
Determining the sign of ∆𝑯
Molten gold poured into a mold solidifies at
atmospheric pressure. With the gold defined as the
system, is the solidification an exothermic or
endothermic process?
𝐶 𝑠 + 𝑂2 𝑔 → 𝐶𝑂2 𝑔 ∆𝐻 = − 393.5 𝑘𝐽
𝐶𝑂2 𝑔 → 𝐶 𝑠 + 𝑂2 𝑔 ∆𝐻 = 393.5 𝑘𝐽
• Reversing the reaction changes the sign but not

the value of ∆𝐻.
A typical example of a thermochemical equation that is
endothermic is the conversion of methyl alcohol to
carbon monoxide and hydrogen. Note that ∆𝐻 is
positive or ∆𝐻>O
𝐶𝐻3 𝑂𝐻 𝑔 → 𝐶𝑂 𝑔 + 2𝐻2 𝑔
∆𝐻 = + 90.7 𝑘𝐽 (𝑒𝑛𝑑𝑜𝑡ℎ𝑒𝑟𝑚𝑖𝑐)
On the other hand, an exothermic process, such

as formation of hydrofluoric acid from hydrogen
and fluorine, is represented by following
equation:
𝐻2 𝑔 + 𝐹2 𝑔 → 2𝐻𝐹 𝑔
∆𝐻 = − 557 𝑘𝐽 (𝑒𝑥𝑜𝑡ℎ𝑒𝑟𝑚𝑖𝑐)
To show that enthalpy is an extensive property,
meaning, the value of ∆𝐻 is dependent on the amount
of reactants consumed, let us consider the combustion
of acetone, 𝐶3 𝐻6 𝑂 (molar mass = 58 g/mole).
𝑪𝟑 𝑯𝟔 𝑶 𝒍 + 𝟒𝑶𝟐 𝒈 → 𝟑𝑪𝑶𝟐 𝒈 + 𝟑𝑯𝟐 𝑶 𝒍 ∆𝑯 = −𝟏𝟕𝟗𝟎 𝒌𝑱
The thermochemical equation shows that burning 1

mole of acetone in the presence of 4 moles of oxygen
gas releases 1790 kJ of heat. This information can be
considered as a stoichiometric relation:
1 mole 𝑪𝟑 𝑯𝟔 𝑶 = 1790 kJ
Sample Problem 4
Calculate the amount of heat released during the

combustion of:
a. 0.30 mol C3 H6 O
b. 100 g of C3 H6 O
Sample Problem 4

combustion of:
a. 0.30 mol C3 H6 O
− 1790 𝑘𝐽
Heat = 0.30 𝑚𝑜𝑙 𝐶3 𝐻6 𝑂 𝑥 = - 537 kJ
1 𝑚𝑜𝑙 𝐶3 𝐻6 𝑂
Sample Problem 4

combustion of:
b. 100 g of C3 H6 O
1 𝑚𝑜𝑙𝐶3 𝐻6 𝑂 − 1790 𝑘𝐽
Heat = 100 𝑔 𝐶3 𝐻6 𝑂 𝑥 𝑥
58 𝑔 𝐶3 𝐻6 𝑂 1 𝑚𝑜𝑙 𝐶3 𝐻6 𝑂
= - 3086 kJ
Sample Problem 5
Answer: - 14.4 kJ
Calorimetry
• The value of ∆𝐻 can be determined experimentally by
measuring the heat flow accompanying a reaction at
constant pressure.
• The measurement of heat flow is calorimetry.
• A device used to measure heat flow is a calorimeter.
Heat Capacity and Specific Heat
• The more heat an object gains, the hotter it gets.
• The temperature change experienced by an object when
it absorbs a certain amount of heat is determined by its
heat capacity, denoted C.
• The heat capacity of one gram of a substance is called
its specific heat capacity, or merely its specific heat, 𝐶𝑠
.
Specific Heat (specific heat capacity), 𝑪𝒔
𝑞
𝐶𝑠 =
𝑚 × ∆𝑇
Where:
q = is the amount of heat absorbed or release
m = mass of the solution in grams (essentially mass of water)
∆𝑻 = change in temperature 𝒕𝒇𝒊𝒏𝒂𝒍 − 𝒕𝒊𝒏𝒊𝒕𝒊𝒂𝒍 in K or ℃
Amount of Heat, 𝐪
𝑞 = 𝑚 𝐶𝑠 ∆𝑇
Sample Problem 6
Amount of heat absorbed (q)
A 466 gram sample of water is heated from 8.50 oC to

74.60 oC. Calculate the amount of heat absorbed by the
water.
𝑞 = 𝑚 𝐶𝑠 ∆𝑇
= (466 g)(4.18 J/g oC) (74.60 - 8.50 oC)
= 1.29 x 105
= 1.29 kJ
Sample Problem 7
Amount of heat absorbed (q)
Calculate the amount of heat required to raise the

temperature of 165 g of water from 12.0 °C to 88.0 °C.
Answer: 52.4 kJ
Sample Problem 8
Large beds of rocks are used in some solar-heated homes
to store heat. Assume that the specific heat of the rocks is
0.82 𝐽Τ𝑔. 𝐾. Calculate the quantity of heat absorbed by
50.0 kg of rocks of their temperature increases by 12℃.
Sample Problem 9
What temperature change would these rocks undergo if
they emitted 450 𝑘𝐽 of heat absorbed by 50.0 kg rocks?
Assume that the specific heat of the rocks is 0.82 𝐽Τ𝑔. 𝐾.
Hess’s Law
It is often possible to calculate the ∆𝐻 for a reaction
from the tabulated ∆𝐻 values of other reactions. Thus, it
is not necessary to make calorimetric measurements for
all reactions.
We can burn carbon directly to carbon dioxide in one

step only.
C (s) + O2(g) —> CO2 (g) ΔH = - 393.509 kJ

Hess’s Law
If a reaction is carried out in a series of steps, for the
overall reaction equals the sum of the enthalpy changes
for the individual steps.
Or we can do it in two steps:

carbon to carbon monoxide, then
carbon monoxide to carbon dioxide.
C (s) + ½ O2 (g) —> CO (g) ΔH = - 110.524 kJ
CO (g) + ½ O2 (g) —> CO2(g) ΔH = - 282.985 kJ
The net equation is
C (s) + O2 (g) —> CO2 (g) ΔH = - 393.509 kJ
 Cancel CO because it appears on both sides of the equation
Hess’s Law
𝐶𝐻4 𝑔 + 2 𝑂2 𝑔 → 𝐶𝑂2 𝑔 + 2 𝐻2 𝑂 𝑔 ∆𝐻 = −802 𝑘𝐽

(Add) 2 𝐻2 𝑂 𝑔 → 2 𝐻2 𝑂 𝑙 ∆𝐻 = −88 𝑘𝐽
𝐶𝐻4 𝑔 + 2 𝑂2 𝑔 + 2 𝐻2 𝑂 𝑔 → 𝐶𝑂2 𝑔 + 2 𝐻2 𝑂 𝑙 + 2𝐻2 𝑂 𝑔 ∆𝐻 = −890 𝑘𝐽
The net equation is
𝐶𝐻4 𝑔 + 2 𝑂2 𝑔 → 𝐶𝑂2 𝑔 + 2 𝐻2 𝑂 𝑙 ∆𝐻 = −890 𝑘𝐽

Sample Problem 10
Calculate the enthalpy change (ΔH) of methane (CH4).
Answer: C (s) + 2 H2 (g) —> CH4 (g) ΔH = - 74.8 kJ

Sample Problem 11
Sample Problem 12
Sample Problem 13
44
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Thermochemistry

Chem 11 | General Chemistry II 9

• Most chemical reactions in laboratories and even in

• The term enthalpy, from the Greek word,

• Reversing the reaction changes the sign but not

On the other hand, an exothermic process, such

𝑪𝟑 𝑯𝟔 𝑶 𝒍 + 𝟒𝑶𝟐 𝒈 → 𝟑𝑪𝑶𝟐 𝒈 + 𝟑𝑯𝟐 𝑶 𝒍 ∆𝑯 = −𝟏𝟕𝟗𝟎 𝒌𝑱

The thermochemical equation shows that burning 1

𝑪𝟑 𝑯𝟔 𝑶 𝒍 + 𝟒𝑶𝟐 𝒈 → 𝟑𝑪𝑶𝟐 𝒈 + 𝟑𝑯𝟐 𝑶 𝒍 ∆𝑯 = −𝟏𝟕𝟗𝟎 𝒌𝑱

Calculate the amount of heat released during the

Calculate the amount of heat released during the

Calculate the amount of heat released during the

Amount of heat absorbed (q)

A 466 gram sample of water is heated from 8.50 oC to

Amount of heat absorbed (q)

Calculate the amount of heat required to raise the

We can burn carbon directly to carbon dioxide in one

C (s) + O2(g) —> CO2 (g) ΔH = - 393.509 kJ

Or we can do it in two steps:

𝐶𝐻4 𝑔 + 2 𝑂2 𝑔 → 𝐶𝑂2 𝑔 + 2 𝐻2 𝑂 𝑔 ∆𝐻 = −802 𝑘𝐽

𝐶𝐻4 𝑔 + 2 𝑂2 𝑔 + 2 𝐻2 𝑂 𝑔 → 𝐶𝑂2 𝑔 + 2 𝐻2 𝑂 𝑙 + 2𝐻2 𝑂 𝑔 ∆𝐻 = −890 𝑘𝐽

The net equation is

𝐶𝐻4 𝑔 + 2 𝑂2 𝑔 → 𝐶𝑂2 𝑔 + 2 𝐻2 𝑂 𝑙 ∆𝐻 = −890 𝑘𝐽

Answer: C (s) + 2 H2 (g) —> CH4 (g) ΔH = - 74.8 kJ

DEPARTMENT OF EDUCATION-BUREAU OF CURRICULUM DEVELOPMENT

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