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Week 3 : Thermochemical Equations

I. Introduction
Energy change in a chemical reaction is related to the equilibrium conditions. By studying
the energy changes, it is possible to predict whether a reaction will take place or not, and to
determine the conditions under which the reaction will proceed best. A thermochemical
equation is a chemical equation that includes the amount of energy, in the form of heat that is
transferred in the reaction. This heat, usually expressed in kilocalories (kcal) or kilojoules (kJ), can
be considered as a product or a reactant in the balanced equation.
A reaction that gives off heat is called an exothermic reaction, and the one that absorbs
heat is called an endothermic reaction.

II. Objectives
At the end of the week, you should be able to:
1. Calculate heat changes using standard heats of formation.
2. Perform common Laboratory operations.

III. Thermochemical Equations

If you mix calcium oxide with water, an exothermic reaction takes place. The water in the
mixture becomes warm. This reaction occurs when cement, which contains calcium oxide, is
mixed to make concrete. When 1 mol of calcium oxide reacts with 1 mol of water, 1 mol of
calcium hydroxide forms and 65.2 kJ of heat is released. When you write down the chemical
equation representing this reaction, heat change may be included as product of the reaction.

CaO(s) + H2O(l) → Ca(OH)2(s) + 65.2 kJ

An equation that includes the heat change is called a thermochemical equation. A heat of
reaction is the heat change for the equation exactly as t is written. Heats of reaction may be
represented by ΔH, which is heat change at constant pressure. The physical states of the
reactants and products must also be given. The standard conditions are that the reaction is
carried out at 101.3 kPa (1 atmosphere) and the reactants and products are in their usual physical
states at 250C.
The heat of reaction, or ΔH, in the above example is -65.2 kJ. Each mole of calcium oxide
and water that react to form calcium hydroxide produces 65.2 kJ of heat. Another way of writing
down the reaction will be:

CaO(s) + H2O(l) → Ca(OH)2(s) ΔH = -65.2 kJ

Other reactions absorb heat from the surroundings. One example is when baking soda
(sodium bicarbonate) decomposes when it is heated, making it useful in baking. The carbon
dioxide released in the reaction causes the cake to rise while baking. This process is
endothermic, and the heat of reaction is 129 kJ.

2NaHCO3(s) + 129 kJ → Na2CO3(s) + H2O(g) + CO2(g)

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ΔH for endothermic reactions is positive. The reaction can also be written as:

2NaHCO3(s) → Na2CO3(s) + H2O(g) + CO2(g) ΔH = 129 kJ

Note:
- The sign of ΔH indicates whether the reaction is endothermic ( positive ΔH ), or exothermic
(negative ΔH)
- In interpreting a thermochemical equation, the coefficients represents number of moles of the
substances
- The phases (physical states) of all species must be identified using the symbols (s) for solids, (l)
for liquids, (g) for gases and (aq) for aqueous
- The value for ΔH applies when the reactants and products are at the same temperature, taken
at 250C unless specified otherwise.
- Stoichiometric calculations may be solved by applying ratio and proportion method to the
given thermochemical equations. You may express given amounts of substances in moles
before applying ratio and proportion method. ( wt=nMW; n = wt/MW; MW is the formula
weight)
- When you use the reverse form of the reaction, take the opposite sign for ΔH

Example 1.9 .
Using the equation: 2NaHCO3(s) → Na2CO3(s) + H2O(g) + CO2(g) ΔH = 129 kJ
Calculate the kilojoules of heat required to decompose 2.24 mol NaHCO 3(s)

Solution:
2.24 mol x
2NaHCO3(s) → Na2CO3(s) + H2O(g) + CO2(g) ΔH = 129 kJ
2 mol 129 kJ
By ratio and proportion:
.
=

( . )( )
x = cross multiply and solve for x

x = 144.48 kJ unit mol cancels out

Answer: 144.48 kJ, heat required to decompose 2.24 mol NaHCO 3

Example 1.10
When carbon disulfide is decomposed from its elements, heat is absorbed. Calculate amount of
heat ( in kJ ) absorbed when 5.66 g of carbon disulfide is formed.

C(s) + 2S(s) → CS2(l) ΔH = 89.3 kJ

Solution:

We let x = amount of heat absorbed in the formation of 5.66g CS 2

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5.66g =0.074mol x n=wt/MW; MW=76g/mol

C(s) + 2S(s) → CS2(l) ΔH = 89.3 kJ n= 5.66g/(76g/mol)

1 mol 89.3 kJ = 0.074 mol
By ratio and proportion:
.
=
.

( . )( . )
x = cross multiply and
solve for x
x = 6.6 kJ unit mol cancels out

Answer: 6.6 kJ, heat absorbed in the formation of 5.66g CS2

IV. Heats of Formation

[1] The standard heats of formation ( ΔHf0 ) of a compound is the change in
enthalpy that accompanies the formation of one mole of a compound from its elements with all
substances in their standard states at 25 0C.
The ΔHf0 of a free element in its standard state is arbitrarily set at zero. For example, ΔHf0
Is zero for diatomic molecules H2(g), N2(g), O2(g), F2(g), Cl2(g), Br2(l), and I2(g). ΔHf0 is also zero for the
graphite form of carbon, C(s,graphite) and all other elements existing as free elements in the
reaction.

[1]Table 1.5 Standard Enthalpies of Formation at 25C (kJ/mol) of Compounds at 1 atm, Aqueous Ions at 1 M
p.203, Chemistry for Engg Students by Masterton W.,et.al.

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Enthalphies of formation can be used to calculate ΔH0 for a reaction. We may apply this
general rule: [1] The standard enthalpy of change, ΔH0, for a given thermochemical equation is
equal to the sum of the standard enthalpies of formation of the product compounds minus the
sum of the standard enthalpies of formation of the reactant compounds.
ΔH0rxn = Σ ΔHf 0 products - Σ ΔHf 0 reactants

Rules applied when using this equation:

1. Elements in their standard states can be omitted, because their heats of formation
are zero.
2. The coefficients of products and reactants should be multiplied to the ΔH f 0 of the
substances when it is greater than 1, because ΔHf 0 values given are per one mole of
the compound.

Example 1.11
Using ΔHf values, calculate ΔHrxn for the reaction of gaseous carbon monoxide with oxygen to
form gaseous carbon dioxide using ΔHf 0 values from the table.
2CO(g) + O2(g) → 2CO2(g)

Solution:
From the table: ΔHf 0 CO(g) = -110.5 kJ/mol
ΔHf 0 CO2(g) = -393.5 kJ/mol
ΔHf 0 O2(g) = 0

Applying the equation:

ΔH0rxn = Σ ΔHf 0 products - Σ ΔHf 0 reactants
ΔH rxn = ( 2 x ΔHf 0 CO2(g) ) - [ (2 x ΔHf 0 CO(g)) + ( ΔHf 0 O2(g)) ] using ΔHf 0values
0

= [ 2 x (-393.5kJ) ] - [ (2 x -110.5) kJ + 0 ] multiply by coeff.

= (-787.0 kJ) – ( -221.0 kJ ) from equation
= - 566.0 kJ

Answer: ΔHrxn 0 = -566.0 kJ

Example 1.12
Given the reaction 2Al2O3(s) → 4 Al(s) + 3O2(g) ΔH 0 = 3351.4 kJ
a. What is the heat of formation of aluminum oxide?
b. What is ΔH 0 for the formation of 12.50 g of aluminum oxide?

Solution:
a. Using : ΔHf 0 Al(s) = 0
ΔHf 0 O2(g) = 0
ΔHrxn = 3351.4 kJ
ΔH0rxn = Σ ΔHf 0 products - Σ ΔHf 0 reactants using ΔH0rxn equation
0 0 0 0
ΔH rxn = [ (4x ΔH f Al(s)) + (3x ΔH fO2(g))] – [2xΔH fAl2O3(s)]
3351.4 kJ = [ (4 x 0) + (3 x 0)] – [2xΔH0fAl2O3(s)] substituting values
3351.4 kJ = [ 0 + 0 ] – [2xΔH0fAl2O3(s)]

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3351.4 kJ = 0 – [2 x ΔH0fAl2O3(s)]
3351.4 kJ = – [2 x ΔH0fAl2O3(s)]
– [2 x ΔH0fAl2O3(s)] = 3351.4 kJ
.
ΔH0fAl2O3(s) = solving for the unknown

ΔH0fAl2O3(s) = -1675.7 kJ

Answer: ΔH0fAl2O3(s) = -1675.7 kJ, heat of formation of Al2O3(s)

b. Formation reaction for Al2O3(s) :

4 Al(s) + 3O2(g) → Al2O3(s) ΔH 0 = -3351.4 kJ -ΔH 0 for reverse reaction

12.5g=0.12mol x
4 Al(s) + 3O2(g) → Al2O3(s) ΔH 0 = -3351.4 kJ n=wt/MW
1 mol -3351.4 kJ wt=12.5 g
MW = 102g/mol
n=12.5g/(102g/mol)=0.12mol
by ratio and proportion:

.
=
.

( . )( . )
x = cross multiply and solve for x

x = -402.17 kJ unit mol cancels out

Answer: -402.17 kJ, heat needed for the formation of 12.5 g Al2O3(s)

Example 1.13
[1] The Bunsen burners in your labs are fueled by natural gas, which is mostly methane, CH 4. The
thermochemical equation of for the combustion ( burning in oxygen ) of methane is
CH4(g) + 2O2g) → CO2(g) + 2H2O(l) ΔH = -890.3 kJ
a. Calculate ΔH when 5.0 g of CH4 react with an excess of oxygen.
b. Calculate ΔH when 2.0 L of CH4 at 490C and 782 mmHg react with an excess of oxygen.
c. Calculate ΔH when 2.0 L of CH4 react with 5.0 L of O2 in a reaction vessel kept at 490C and 782 mmHg.

Solution:
a. let x = ΔH when 5.0 g of CH4 react with an excess of oxygen

5.0 g = 0.31 mol x n=wt/MW; MW=16g/mol

CH4(g) + 2O2g) → CO2(g) + 2H2O(l) ΔH = -890.3 kJ n= 5g/(16g/mol)
1 mol -890.3 kJ n= 0.31 mol
by ratio and proportion:
.
=
.

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( . )( . )
x = cross multiply, solve for x

x = -276 kJ unit mol cancels out

Answer: ΔH = -276 kJ

.
b. n for CH4 is solved using ideal gas law : PV = nRT , where R =

n= P = (782mmHg)( ) = 1.03 atm

V = 2.0 L
T = 490C + 273 = 322 K

( . )( . )
n= substitute into formula
. ( )

n = 0.078 mol units atm,L,K cancels

0.078 mol x
CH4(g) + 2O2g) → CO2(g) + 2H2O(l) ΔH = -890.3 kJ
1 mol -890.3 kJ

by ratio and proportion:

.
=
.

( . )( . )
x = cross multiply, solve for x

x = -69.44 kJ unit mol cancels

Answer: ΔH = -69.44 kJ

c. This is a limiting reactant problem, since volume of both reactants is given at constant pressure and
temperature. Solve volume of CO2 if CH4 is the limiting reagent and again if O2 as limiting agent. Choose
the smaller value to determine the actual limiting reagent.

2.0 L a
CH4(g) + 2O2g) → CO2(g) + 2H2O(l) ΔH = -890.3 kJ
1.0 L 1.0 L use Volume : mol =volume based
on coefficients
.
= by ratio and proportion
. .

( . )( . )
a = cross multiply, solve for a
.

a = 2.0 L CO2 , using CH4 as LR

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5.0 L b
CH4(g) + 2O2g) → CO2(g) + 2H2O(l) ΔH = -890.3 kJ
2L 1.0 L use Volume : mol =volume based
on coefficients

.
= by ratio and proportion
. .

( . )( . )
b = cross multiply, solve for b
.

b = 2.5 L CO2, using O2 as LR

CH4 is the limiting reagent. Volume = 2.0 L based on smaller CO2 volume

n= P = (782mmHg)( ) = 1.03 atm

V = 2.0 L
T = 490C + 273 = 322 K

( . )( . )
n= substitute into formula
. ( )

n = 0.078 mol units atm,L,K cancels

0.078 mol x
CH4(g) + 2O2g) → CO2(g) + 2H2O(l) ΔH = -890.3 kJ
1 mol -890.3 kJ

by ratio and proportion:

.
=
.

( . )( . )
x = cross multiply, solve for x

x = -69.44 kJ unit mol cancels

Answer: ΔH = -69.44 kJ

V. Learning Activity 1.3

1. What information is given in a thermochemical equation?

2. What special name is given to a heat change at constant pressure
3. Write thermochemical equations for the formation of one mole of the following compounds
from the elements in their native states at 250C and 1 atm.
a. Solid potassium chlorate

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b. Liquid carbon tetrachloride

c. Gaseous hydrogen iodide
d. Solid silver(I) oxide

VI. Exercise 1.3

1. Use standard heats of formation (ΔHf0) to calculate the change in enthalpy for the following
reactions:
a. 2C(s,graphite) + O2(g) → 2CO(g)
b. 2H2O2(l) → 2H2O(l) + O2(g)
c. 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
2. Limestone, CaCO3, when subjected to a temperature of 9000C in a kiln, decomposes to
calcium oxide and carbon dioxide. How much heat is evolved or absorbed when one gram of
limestone decomposes? ( At.mass: Ca = 40; C =12; O =16 )
3. Given the reaction: 2Cr2O3(s) → 4Cr(s) + 3O2(g) ΔH = 2269.4 kJ
a. What is the heat of formation of chromium (III) oxide?
b. What is ΔH for the formation of 13.65 g of chromium (III) oxide?
( At.mass: Cr = 52 O = 16 )
4. When hydrazine, N2H4(g) , reacts with oxygen, nitrogen gas and steam are formed.
a. Write the thermochemical equation for the reaction.
b. How much heat is evolved or absorbed if 1.683 L of steam at 1250C and 772 mmHg are
obtained?

VII. Quiz
Submit test booklets to the testing center before taking the examination. Schedule will be announced to
the class group. Coverage for Quiz 3 will be ΔHrxn from heats of formation and stoichiometry involving
thermochemical equations.

VIII. Laboratory
Part of the Pre-Lab Activity will be the use of basic instruments in the lab such as the Bunsen burner,
platform balance, digital balance, etc. and common laboratory operations like filtration, evaporation,
decantation and distillation. Video demo and instructions will be given by your instructor. Submission of
written reports will be announced to the class group.

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Week 4 : Hess Law;

First and Second Law of Thermodynamics

I. Introduction
Most reactions occur in a series of steps. You may need to know the heat of reaction for
an intermediate step, but it is impossible for you to obtain the value directly. Hess law makes it
possible to measure a heat of reaction indirectly. Even when a direct measurement cannot be
made, the heat of reaction can still be determined.

II. Objectives
At the end of the week, you should be able to:
1. Perform calculations of enthalpies of reaction using Hess Law
2. Apply the basic principles of the first and second law of thermodynamics and
understand how it is related to the principles of thermochemistry.

III. Hess Law of Heat Summation

Elemental carbon exists as both graphite and diamond at 25 0C. Because graphite is more
stable than diamond, you would expect the following process to take place.
Cdiamond → Cgraphite
The conversion of diamond to graphite takes millions and millions of years. This enthalpy change
cannot be measured directly because the reaction is too slow. Hess Law may be applied to
calculate heat of reaction.
[1] The value of ΔH for a reaction is the same whether it occurs in one step or in a series of
steps. If a thermochemical equation can be expressed as the sum of two or more equations,
Equation = equation (1) + equation (2) + …
then ΔH for the overall equation is the sum of the ΔHs for the individual equations:
ΔH = ΔH1 + ΔH2 + …
This relationship is referred to as Hess Law, named after Germain Hess (1802-1850),
professor of chemistry at the University of St. Petersburg, who deduced it in 1840. Hess law is very
convenient for obtaining values of ΔH for reactions that are difficult to carry ot in a calorimeter.
Consider the formation of the toxic gas carbon monoxide from the elements
C(s) + ½ O2(g) → CO(g)
It is difficult to measure ΔH for this reaction because when carbon burns, the major product is
always carbon dioxide, CO2. It is possible, however, to calculate ΔH using thermochemical data
for two other reactions that are readily carried out in the laboratory.

Note:
Rules followed when applying Hess Law of Heat Summation
1. When the reaction is multiplied by a certain number, ΔH value should also be multiplied by the
same number.
2. When the reaction is divided by a certain number, ΔH value should also be divided by the
same number.
3. When you take the reverse form of the reaction, assign the opposite sign for ΔH value

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4. Add the thermochemical equations by adding the reactants found before the arrow sign and
adding the products found after the arrow sign. The same substances (with same state)
s will
cancel out.
5. ΔH for the reaction is the sum of the final values of ΔH for the equations.
6. Use the final equation to be obtained as basis for coefficients and arrangement of the
equations before adding.

Example 1.14
Carbon monoxide, CO, a poisonous g as, can be obtained by burning carbon in a limited amount
of oxygen. Given the following reactions:
(1) C(s) + O2(g) → CO2(g) ΔH = -393.5 kJ
(2) 2CO(g) + O2(g) → 2CO2(g) ΔH = -566.0 kJ
Calculate ΔH
H for the reaction
C(s) + ½ O2(g) → CO(g)

Solution:
(1) : C(s) + O2(g) → CO2(g) ΔH = -393.5 kJ eqn1 no change
rev (2)x ½ : CO2(g) → CO(g) + ½ O2(g) ΔH = 566.0 x ½ = 283 kJ reverse,divide by2
C(s) + ½ O2(g) → CO(g) ΔH = -110.5 kJ adding, CO2 cancels
½ O2(g) remains

Example 1.15
Given the following equations and Ho values, determine the heat of reaction (kJ) at 298 K for
the reaction:
B2H6(g) + 6 Cl2(g) 2 BCl3(g) + 6 HCl(g)

(1) BCl3(g) + 3 H2O(l) H3BO3(g) + 3 HCl(g) Ho = -112.5 kJ

(2) B2H6(g) + 6 H2O(l) 2 H3BO3(g) + 6 H2(g) Ho = -493.4 kJ
(3) 1/2 H2(g) + 1/2 Cl2(g) HCl(g) Ho = -92.3 kJ

Solution:

rev(1) x2 : 2 H3BO3(g) + 6 HCl(g) → 2 BCl3(g) + 6 H2O(l) ΔH=(112.5)(2) = 225 kJ

(2) : B2H6(g) + 6 H2O(l) → 2 H3BO3(g) + 6 H2(g) ΔH = -493.4 kJ = -493.4 kJ
(3) x12: 6 H2(g) + 6 Cl2(g) → 12HCl(g) ΔH=(-92.3)(12)=
92.3)(12)= -1107.6 kJ
B2H6(g) + 6 Cl2(g) 2 BCl3(g) + 6 HCl(g) ΔH = -1376 kJ

Note: Substances with the same color cancels out. They should be in the same state. For HCl,
6 mol cancels out on the left side, with 6 mol HCl (12 – 6 = 6 ) remaining on the right side. The final
ΔH
H for the reaction will be the sum of the ΔH for each of the three equations.

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IV. First Law of Thermodynamics

The First Law of Thermodynamics is simply the Law of Conservation of Energy, which
states that energy cannot be created nor destroyed. All small amounts of matter can be
converted to energy. The laws of conservation of matter and energy are often combined to state
that matter-energy cannot be created nor destroyed. This leads us to the statement that the
total amount of matter-energy in the universe is constant. The heat produced in an exothermic
reaction is due to a very small amount of matter being converted to energy.
This First Law of Thermodynamics accounts for all the known facts concerning
thermochemical equations. For example, since energy must be conserved, he sum of all the
heats of reaction must be equal to the overall heat of reaction, as stated in Hess’s Law. Also, this
accounts for the fact that ΔHrxn is equal to the sum of ΔHf of products minus reactants.
The difference between ΔE and ΔH is also a consequence of the first law; that is, at
constant volume, no work is done and thus ΔE is measured by the total amount of heat energy
released in the reaction. At constant pressure however, some of the energy released is used to
do work against the atmosphere; therefore, what is measured is the change in heat content
(enthalpy), ΔH. Another way of expressing this relationship between the total energy change, or
heat flow (Q), is :
ΔE = Q - W
Where Q is the heat flow and W is the work done against the surroundings. Since heat flow
measures the amount of energy absorbed ( that is, if Q is positive, the reaction is endothermic),
the total energy change (ΔE) is measured by the heat flow (Q) minus the work done (W).
For example, if 836.8 kJ of heat energy is absorbed by a system and 209.2 kJ of work is
done on the surroundings, the change in energy is
ΔE = 836.8 kJ - 209.2 kJ = 627.6 kJ
The energy of the system has increased by 627.6 kJ.

Q W ΔE = Q + W Remarks
I + + +
heat absorbed work done on energy absorbed
by the system the system by the system
II + - depends on
heat absorbed work done by + or - the magnitude
by the system the system of Q and W
III - - -
heat given off work done by energy given off
by the system the system by the system
IV - + depends on
heat given off work done on + or - the magnitude
by the system the system of Q and W
Table 1.6 Heat, Work, Energy

In applying the first law of thermodynamics, note that Q and W are positive when the
heat or work enters the system from the surroundings. If the transfer is in the opposite direction,
from system to surroundings, Q and W are negative. If work is done on the system or if heat is
added to it, its energy increases.

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Example 1.16
Calculate ΔE of a gas for the following processes where the gas
(a) absorbs 50 J of heat and does 18 J of work by expanding.
(b) evolves 40 J of heat and has 62 J of work done on it as it contracts.

Solution:
(a) Q is positive ( heat absorbed )
W is negative ( work done by the system )

Applying ΔE = Q + W

ΔE = 50 J + ( -18 J) = 32 J

Answer: 32 J

(b) Q is negative ( heat is evolved or given off )

W is positive ( work is done on the system; enters the system )

Applying ΔE = Q + W

ΔE = -40 J + 62 J = 22 J

Answer: 22 J

V. Second Law of Thermodynamics

If ΔH is negative ( heat released or reaction is exothermic ), there will be a good chance
that the reaction will go spontaneously. This is not always true, however, and there are reactions
for which ΔH is positive (endothermic) that go spontaneously. There is therefore another factor
involved, called the [2] entropy(ΔS) , which is the randomness or disorder of the sytem. At
constant pressure, the total energy change is equal to the change in enthalpy (ΔH) minus the
work done against the atmosphere. At constant temperature, the total amount of energy
available to do work, called the [2] free energy, (ΔG), is equal to ΔH minus the change in entropy
multiplied by the absolute temperature. This can be expressed as

ΔG = ΔH - TΔS

A reaction will only occur spontaneously if ΔG is negative. Recalling that a negative sign
means energy is given off by the system, to determine if a reaction will take place spontaneously,
we can calculate ΔG from tables of ΔH and ΔS values and apply the following rules:

1. If ΔG is ( - ), the reaction is spontaneous as written.

2. If ΔG is ( + ), the reverse reaction is spontaneous.
3. If ΔG is zero, the reaction is at equilibrium ( this is when the rate at which the
forward reaction is takes place is equal to the rate at which the reverse reaction is
taking place.

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Table 1.6 Entropy (ΔS ) values of some common substances

Substance ΔS, kcal/mol-K ΔS, kJ/mol-K

H2O(g) 0.0451 0.189
H2O(l) 0.0167 0.087
H2(g) 0.0312 0.130
Cl2(g) 0.0533 0.221
N2(g) 0.0458 0.189
O2(g) 0.0490 0.204
NH3(g) 0.0460 0.192
CO(g) 0.0473 0.197
CO2(g) 0.0511 0.213
SO2(g) 0.0594 0.247
C2H2(g) 0.0480 0.200
C2H4(g) 0.0525 0.217
C2H6(g) 0.0549 0.225
CH3OH(g) 0.0568 0.234
CH3OH(l) 0.0303 0.125
[2] Entropy (ΔS) Table; p.229

Example 1.17
Calculate (a) ΔH , (b) ΔS , and (c) ΔG for the following reaction, at 25 0C, and tell if the reaction
will go spontaneously.
C2H4(g) + 3 O2(g) → 2 CO2(g) + 2 H2O(g)

Solution:

(a) ΔHrxn = Σ ΔHfproducts - Σ ΔHfreactants

= [ 2 ( ΔHf CO2(g)) + 2 (ΔHf H2O(g)) ] - [ΔHf C2H4(g) + 0 ]
= [ 2 (-393.5 kJ) + 2 ( -241.8 kJ) ] - ( 52.3 kJ ) refer to ΔHf table
= [ -787 kJ + -483.6 kJ ] - 52.3 kJ
= - 1270.6 kJ - 52.3 kJ
= -1322.9 kJ

Answer: ΔH = -1322.9 kJ

(b) ΔS = Σ ΔSproducts - Σ ΔSreactants

= [ 2 ( ΔS CO2(g)) + 2 (ΔS H2O(g)) ] - [ΔS C2H4(g) + ΔS O2(g) ]
= [ 2 (0.213) + 2 (0.189) ] kJ/K - [ 0.217 + 0.204 ] kJ/K refer to ΔS table
= [ 0.426 + 0.378 ] – (0.421 ) kJ/K
= ( 0.804 – 0.421 ) kJ/K
= 0.383 kJ/K

Answer: ΔS = 0.383 kJ/K

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(c ) ΔG = ΔH - TΔS
= -1322.9 kJ - ( 298K)(0.383kJ/K) using answers in (a) and (b);
T = 250C, in K: T = 25+273 = 298K
= -1322.9 kJ - 114.1 kJ unit K cancels
= -1437 kJ

Answer: ΔG = -1437 kJ

The reaction will go spontaneously. If ΔG is negative, reaction will proceed

spontaneously.

Example 1.18
For the reaction, H2O(l) → H2O(g) , calculate ΔG at (a) 200C , (b) 1580C and (c) 1800C.

Solution:

Quantities needed to be solved before ΔG : ΔHrxn , ΔS

ΔHrxn = Σ ΔHfproducts - Σ ΔHfreactants

= [ ΔHf H2O(g) ] - [ ΔHf H2O(l) ]
= ( -241.8 kJ ) - ( -285.8 kJ )
= 44 kJ

ΔS = Σ ΔSproducts - Σ ΔSreactants
= [ ΔS H2O(g) ] - [ ΔS H2O(l) ]
= ( 0.189 kJ/K) - ( 0.087 kJ/K)
= 0.102 kJ/K

(a) ΔG = ΔH - TΔS at T = 200C T = 20 + 273 = 293K

= 44 kJ - (293K)(0.102 kJ/K)
= 44 kJ - 35.75 kJ
= 8.25 kJ
Answer: ΔG = 8.25 kJ

(b) ΔG = ΔH - TΔS at T = 1580C T = 158 + 273 = 431K

= 44 kJ - (431K)(0.102 kJ/K)
= 44 kJ - 44 kJ
= 0 kJ
Answer: ΔG = 0 kJ

(c) ΔG = ΔH - TΔS at T = 1800C T = 180 + 273 = 453K

= 44 kJ - (453K)(0.102 kJ/K)
= 44 kJ - 46.2 kJ
= -2.2 kJ
Answer: ΔG = -2.2 kJ

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Note: At 200C, the reverse reaction takes place spontaneously.

At 1580C, the reaction is at equilibrium.
At 1800C, the reaction takes place spontaneously.

[2] The Second Law of Thermodynamics states that the entropy of the universe is
increasing, and that any spontaneous change is always to a more disordered state. Thus, the
Second Law of Thermodynamics tells us the following things:
1. Some energy absorbed is always going to increase the entropy of the system except at
absolute zero. (At 0 K, the TΔS term would become zero.)
2. The entropy of the univers
universe is increasing.
3. Any spontaneous process is a change to a more disordered or more probable state.
4. At constant temperature and pressure, a change can occur spontaneously only if there
is a decrease in free energy.

VI. Exercise 1.4

1. Given the following equations and Ho values, determine the heat of reaction (kJ) at 298 K
for the reaction:
2 OF2(g) + 2 S(s) SO2(g) + SF4(g)

(1) OF2(g) + H2O(l) O2(g) + 2 HF(g) H = -276.6 kJ

(2) SF4(g) + 2 H2O(l) 4 HF(g) + SO2(g) H = -827.5 kJ
(3) S(s) + O2(g) SO2(g) H = -296.9 kJ

2. Calculate the value of Ho for the following reaction using the given thermochemical
equations:
P4O10(g) + 6 PCl5(g) 10 Cl3PO(g)

(1) 1/4 P4(s) + 3/2 Cl2(g) PCl3(g) H = -306.4 kJ

(2) P4(s) + 5 O2(g) P4O10(g) H = -2967.3 kJ
(3) PCl3(g) + Cl2(g) PCl5(g) H= -84.2 kJ
(4) PCl3(g) + 1/2 O2(g) Cl3PO(g) H = -285.7 kJ

3. For each of the following reactions, calculate ΔH, ΔS and ΔG at 250C, and tell if the reactions
will go spontaneously:
(1) N2(g) + 3H2(g) → 2NH3(g)
(2) 2C2H2(g) + 5O2(g) → 4CO2(g) + 2H2O(g)
(3) 2CH3OH(g) + 3O2(g) → 2CO2(g) + 4H2O(g)

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VII. Quiz
Submit test booklets to the testing center before taking the examination. Schedule will be announced to
the class group. Coverage for Quiz 4 will be Hess Law of Heat Summation, ΔS and ΔG.

VIII. Laboratory
Part(II) of the Pre-Lab Activity will be the common laboratory techniques like measurement of volume,
mass, determination of density of unknown substances, water bath evaporation and fractional
distillation. Video demo and instructions will be given by your instructor. Submission of written reports
will be announced to the class group.

IX. Prelim Exam

Submit test booklets to the testing center before taking the examination. Schedule will be announced to
the class group. Coverage for Prelim Exam will be Chapter 1, Thermochemistry.

CHEMISTRY for ENGINEERS v1.0 by GINA E.DIOCOS, ChE 34