ENERGY AND ENERGY CHANGES

IN CHEMICAL REACTIONS
GENERAL CHEMISTRY 2
COURSE OUTCOME 3
ENERGY
Energy is defined as the capacity to do work and produce heat. It is known and
characterized by its effects because it cannot be seen, touched, smelled, or
weighed.

Work, in chemistry, is defined as directed energy change resulting from a process.

Heat is a particular form of energy that is transferred from a body at high

temperature to one at a lower temperature when they are brought into contact with
each other.
We use the phrase “heat flow” to refer to heat transfer or to heat effects in general.
TYPES OF ENERGY
Kinetic Energy – energy present in a moving object
Potential Energy - energy available by virtue of an object’s position
Radiant Energy - or solar energy, comes from the sun and is
Earth’s primary energy source
Thermal Energy – heat energy, energy associated with the random
motion of atoms and molecules because of raised temperature
Chemical Energy - stored within the structural units of chemical
substances
UNIT OF ENERGY
1 calorie = heat required to raise temp. of 1.00 g of H2O by 1.0 oC.
1000 cal = 1 kilocalorie
1 kcal = 1 Calorie (a food “calorie”)
But we use the unit called the JOULE
1 cal = 4.184 J

James Joule
1818-1889
 THERMOCHEMISTRY is the study of heat change in
chemical reactions.

Did the chemical reaction needed heat or did it gave off

heat?
PRINCIPLES OF HEAT FLOW
Systems and Surroundings
• SYSTEM is that part of the universe on which attention is being
focused
• SURROUNDINGS is that part of the universe which exchange
energy with the system
• 3 Types of Systems:
o Open System – can exchange mass and energy with its surroundings
o Closed System – allows transfer of energy (heat) but not mass
o Isolated system - does not allow the transfer of either mass or energy
3 TYPES OF SYSTEMS
STATE PROPERTIES
State of a system is described by giving its composition,
temperature, and pressure.

For example:
System consists of:
• 50.0 g of H2O(l)
• At 50.0°C
• 1 atm
ENDOTHERMIC AND
EXOTHERMIC PROCESSES
Exothermic Process - any process that gives off heat —that is, transfer of
thermal energy to the surroundings
Endothermic Process - heat has to be supplied to the system by the
surroundings
THERMODYNAMICS is the scientific study of converting
energy usually in the form of heat and work.
LAWS OF THERMODYNAMICS
Zeroth Law
• If two thermodynamic systems are each in thermal equilibrium with a third, then they
are in thermal equilibrium with each other.
First Law: Law of Conservation of Energy
• Energy can neither be created nor destroyed; energy can only be transformed
Second Law:
• The entropy of an isolated system not in equilibrium will tend to increase over time,
approaching a maximum value at equilibrium.
Third Law:
• As temperature approaches absolute zero, the entropy of a system approaches a
constant minimum.

Source: http://physicsforidiots.com/physics/thermodynamics/
FIRST LAW OF
THERMODYNAMICS
FIRST LAW OF
THERMODYNAMICS
“Energy can neither be created nor destroyed; energy can only be converted
from one form to another.”

1) energy contained within a system

- internal energy (state function → pathway independent)

2) energy that can move between a boundary

- heat and work
FIRST LAW OF
THERMODYNAMICS
INTERNAL ENERGY (E)
• energy contained within a system
• Composed of kinetic energy and potential energy contained in a system

*It is impossible to measure all these contributions accurately, so we cannot

calculate the total energy of a system with any certainty. Changes in energy,
on the other hand, can be determined experimentally.
FIRST LAW OF
THERMODYNAMICS

Change in Internal Energy, ∆𝐸:

∆𝑬 = 𝑬𝒇 − 𝑬𝒊
Where ∆𝐸 is the change in internal energy
𝐸𝑓 is the internal energy of the system in its final state
𝐸𝑖 is the internal energy of the system in its initial state
FIRST LAW OF
THERMODYNAMICS
∆𝐸 = 𝑞 + 𝑤
Where: 𝑞 is the heat exchange between the system and the surrounding
𝑤 is the work done on/by the system

* q is positive for endothermic process and negative for exothermic process

* w is positive for work done on the system by the surroundings and negative for work done by
the system on the surroundings
WORK, w
𝑤 =𝐹×𝑑
Where 𝑤 is work
𝐹 is force
𝑑 is distance
This includes mechanical, electrical, and surface work.
 WORK, w

One way to illustrate mechanical work is to study the compression or

expansion of a gas. Example is the internal combustion engine of the
automobile.
Expansion and compression of the cylinders due to the combustion
of the gasoline-air mixture provide power to the vehicle. As it
expands, the gas pushes the piston upward against a constant
opposing external atmospheric pressure P. The work done by the gas
on the surroundings is……
WORK, w

𝑤 = −𝑃∆𝑉
Where: 𝑤 is work
𝑃 is opposing atmospheric pressure
∆𝑉 is the change in volume
WORK: Sample Problem
A certain gas expands in volume from 2.0 L to 6.0 L at constant temperature.
Calculate the work done by the gas if it expands (a) against a vacuum and (b)
against a constant pressure of 1.2 atm.
HEAT, q
Like work, heat is not a state function because they are not properties of a
system. Thus, their values depend on the path of the process and vary
accordingly.
HEAT: Sample Problem
The work done when a gas is compressed in a cylinder is 462 J. During this
process, there is a heat transfer of 128 J from the gas to the surroundings.
Calculate the energy change for this process.
ΔE = q + w
ENTHALPY OF CHEMICAL
REACTION
GENERAL CHEMISTRY 2
COURSE OUTCOME 3
ENTHALPY
Enthalpy (H) is the sum of the internal energy (E) and the product of pressure
and volume (PV) as given by the equation,

H = E + PV

E, P, and V are all state functions. Hence, H is also a state function.

ΔH = ΔE + Δ(PV)
ENTHALPY
Most chemical reactions occur at constant pressure so,

ΔH = ΔE + PΔV
Note that
ΔE = q + w
ΔE = q – PΔV

If we apply this to the equation for the change in enthalpy, we get

ΔH = q
ENTHALPY OF
REACTION, ΔH
Because most reactions are constant-pressure processes, we can equate the
heat change in these cases to the change in enthalpy. For any reaction of the
type,
reactants → products

we define the change in enthalpy, also known as the enthalpy of reaction, ΔH,
as the difference between the enthalpies of the products and the enthalpies of
the reactants:
Endothermic: ΔH is positive
(ΔH>0)
ΔH = Hproducts – Hreactants
Exothermic: ΔH is negative
(ΔH<0)
 THERMOCHEMICAL
EQUATIONS
At 0°C and a pressure of 1 atm, ice
melts to form liquid water.
Measurements show that for every
mole of ice converted to liquid water
under these conditions, 6.01
kilojoules (kJ) of heat energy are
absorbed by the system (ice).
Because the pressure is constant, the
heat change is equal to the enthalpy
change, ΔH.
Therefore, ΔH is a positive quantity
THERMOCHEMICAL
EQUATIONS
Guidelines in writing and interpreting thermochemical equations:
1. When writing thermochemical equations, we must always specify the
physical states of all reactants and products, because they help determine
the actual enthalpy changes.
2. If we multiply both sides of a thermochemical equation by a factor n, then
ΔH must also change by the same factor.
3. When we reverse an equation, we change the roles of reactants and
products. Consequently, the magnitude of ΔH for the equation remains the
same, but its sign changes.
THERMOCHEMICAL
EQUATIONS
Consider the combustion of methane (CH4), the principal component of natural
gas.

Burning natural gas releases heat to the surroundings (exothermic reaction).

Under constant-pressure condition this heat change is equal to enthalpy

change and Δ H must have a negative sign.
What if we double the number of moles of each component in the
chemical reaction, what would happen to the change in enthalpy?
EXAMPLE:
Consider the combustion of C2H6, another example of a principal component of
natural gas.

2C2H6 + 7O2 → 4CO2 + 6H2O

ΔH = -2856 kJ

Determine the enthalpy of reaction for the following:

a) Formation of 1 mol of CO2 by burning C2H6
b) Formation of 6 mol of C2H6 by reacting CO2 with H2O
c) Combination of 1 mol O2 with a stoichiometric quantity of C2H6
EXAMPLE:
Given the thermochemical equation
2SO2(g) + 1 O2(g) 2SO3(g) ΔH = -198.2 kJ/mol

Calculate the heat evolved when 87.9 g of SO2 (molar mass = 64.07 g/mol) is
converted to SO3.
BOARD WORK
Consider the reaction
C3H8 + 5O2 → 3CO2 + 4H2O
ΔH = - 2220 kJ

Calculate the heat evolved in 454 g of C3H8. The molar mass of C3H8 is 44 Da.
CALORIMETRY
GENERAL CHEMISTRY 2
COURSE OUTCOME 3
CALORIMETRY
Calorimetry is the measurement of heat changes.
Depend on:
• Specific heat (s) of a substance is the amount of heat required to raise
the temperature of one gram of the substance by one degree Celsius.
• Heat capacity (C) of a substance is the amount of heat required to raise
the temperature of a given quantity of the substance by one degree
Celsius.
C = ms
m - mass of substance in grams

q = ms Δt q = CΔt
SPECIFIC HEAT OF SOME
COMMON SUBSTANCES

If we know the specific heat and the amount of a

substance, then the change in the sample’s
temperature will tell us the amount of heat that has
been absorbed or released in a particular process.
SAMPLE PROBLEM
A 466-g sample of water is heated from 8.50°C to 74.60°C. Calculate the
amount of heat absorbed by the water.

Solution:
q = msΔt
q = (466g)(4.184 J/g.C)(74.60C – 8.50C)
q = 1.29x105Jx1kJ/1000J
q = 129kJ
BOARD WORK
1. A piece of silver of mass 362 g has a heat capacity of 85.7 J/⁰C. What is
the specific heat of silver?

2. Calculate the amount of heat liberated (in kJ) from 366 g of mercury when
it cools from 77 ⁰C to 12 ⁰C.

3. A 6.22-kg piece of copper metal is heated from 293.65 K to 597.45 K.

Calculate the heat absorbed (in kJ) by the metal.
CONSTANT-VOLUME CALORIMETRY
(combustion reactions)
A calorimeter measures the heat flow of a
chemical reaction or physical change.
• known mass of a compound in a sample
cup
• a sealed bomb filled with oxygen gas
• insulated container filled with known
amount of water
• Ignition wires
• thermometer
• Stirrer
CONSTANT-VOLUME CALORIMETRY
(combustion reactions)
The heat given off by the sample is absorbed by the
water and the bomb. The special design of the
calorimeter enables us to assume that no heat (or mass)
is lost to the surroundings during the time it takes to
make measurements. Therefore, we can call the bomb
and the water in which it is submerged an isolated
system. Because no heat enters or leaves the system
throughout the process, the heat change of the system
( q system ) must be zero and we can write

𝑞𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑞𝑐𝑎𝑙 + 𝑞𝑟𝑥𝑛

𝑞𝑠𝑦𝑠𝑡𝑒𝑚 = 0
𝑞𝑐𝑎𝑙 = −𝑞𝑟𝑥𝑛
𝑞𝑐𝑎𝑙 = 𝐶𝑐𝑎𝑙 ∆𝑡
SAMPLE PROBLEM
It is known that the combustion of 1 g of benzoic acid (C6H5COOH) releases
26.42 kJ of heat. If the temperature rise is 4.6738ºC, then the heat capacity of
the calorimeter is given by
SAMPLE PROBLEM
A quantity of 1.435 g of naphthalene (C10H8), a pungent-smelling substance
used in moth repellents, was burned in a constant-volume bomb calorimeter.
Consequently, the temperature of the water rose from 20.28°C to 25.95°C. If
the heat capacity of the bomb plus water was 10.17 kJ/°C, calculate the heat
of combustion of naphthalene on a molar basis; that is, find the molar heat of
combustion.

Because qsys = qcal + qrxn = 0, qcal = -qrxn .

The heat change of the reaction is -57.66 kJ.
molar mass of naphthalene is 128.2 g
BOARD WORK
1. A quantity of 1.922 g of methanol (molar mass = 32.04 Da) was burned in
a constant-volume calorimeter. Consequently, the temperature of the
water rose by 4.20 °C. If the heat capacity of the bomb plus water was
10.4 kJ/ °C, calculate the molar heat of combustion of methanol.

2. A 0.1375 g sample of solid magnesium (molar mass = 24.31 Da) is burned

in a constant-volume calorimeter that has a heat capacity of 3024 J/ °C.
The temperature increases by 1.126 °C. Calculate the heat given off by the
burning Mg in kJ/g and in kJ/mol.
CONSTANT-PRESSURE CALORIMETRY
(non-combustion reactions)
• A constant-pressure calorimeter can be
constructed from two Styrofoam coffee cups.
• The outer cup helps to insulate the reacting
mixture from the surroundings.
• Two solutions containing the reactants at the
same temperature are carefully mixed in the
calorimeter.
• The heat produced or absorbed by the reaction
can be determined by measuring the temperature
change.
CONSTANT-PRESSURE CALORIMETRY
(non-combustion reactions)
• Because the pressure is constant, the heat
change for the process is equal to the enthalpy
change (ΔH).
SAMPLE PROBLEM
A lead (Pb) pellet having a mass of 26.47 g at 89.98°C was placed in a
constant-pressure calorimeter of negligible heat capacity containing 100.0
mL of water. The water temperature rose from 22.50°C to 23.17°C. What is
the specific heat of the lead pellet?
STANDARD ENTHALPY OF
FORMATION AND REACTION, ∆𝑯°𝒇
GENERAL CHEMISTRY 2
COURSE OUTCOME 3
STANDARD ENTHALPY OF
FORMATION, ∆𝑯°𝒇
a measure of the energy released or consumed when one mole of a substance
is created under standard conditions from its pure elements
Substances are said to be in the standard state at 1 atm, hence the term
“standard enthalpy.”

❖° represents standard-state conditions (1 atm)

❖ “f” stands for formation
By convention, the standard enthalpy of formation of any
element in its most stable form is zero
STANDARD ENTHALPY OF
REACTION, ΔH⁰rxn
aA + bB → cC + dD

where a, b, c, and d are stoichiometric coefficients.

To calculate for the standard enthalpy of reaction,

ΔH⁰rxn = [cΔH⁰f (C) + dΔH⁰f (D)] - [aΔH⁰f (A) + bΔH⁰f (B)]

ΔH⁰rxn = ΣnΔH⁰f (products) – ΣmΔH⁰f (reactants)
STANDARD ENTHALPY OF
FORMATION OF A COMPOUND
DIRECT METHOD
This method of measuring ΔH°f works for compounds that can be readily
synthesized from their elements.
INDIRECT METHOD:
HESS’S LAW

When reactants are converted to products, the change in enthalpy is the same
whether the reaction takes place in one step or in a series of steps.
INDIRECT METHOD:
HESS’S LAW
Determine the standard enthalpy of reaction of CO from the reaction,

2C (graphite) + O2 → 2CO

Note: Burning graphite also produces carbon dioxide, so we cannot directly

measure the enthalpy change. Hence, we employ an indirect route using the
two thermochemical equations below with established standard enthalpy of
reaction.
(1) C (graphite) + O2 → CO2 ΔHf⁰ = -393.5 kJ
(2) 2CO2 → 2 CO + O2 ΔHf⁰ = -566 kJ
SOLUTION
2C (graphite) + O2 → 2CO
__________________________________________________________________
C (graphite) + O2 → CO2 ΔHrxn⁰ = -393.5 kJ
2CO2 → 2 CO + O2 ΔHrxn⁰ = -566 kJ
__________________________________________________________________
How many moles of graphite do we have in the chemical equation being
analyzed in the problem?

Using the rules in thermochemical equations, we can manipulate the given

equation to get the data we want.
SOLUTION
2C (graphite) + O2 → 2CO
__________________________________________________________________
C (graphite) + O2 → CO2 ΔHrxn⁰ = -393.5 kJ
2CO2 → 2 CO + O2 ΔHrxn⁰ = -566 kJ
__________________________________________________________________
2C (graphite) + 2O2 → 2CO2 ΔHrxn⁰ = (-393.5 kJ) x 2 = -787 kJ
2CO2 → 2CO + O2 ΔHrxn⁰ = -566 kJ
________________________________________________________________________
2C (graphite) + 2O2 + 2CO2 → 2CO2 + 2CO + O2 ΔHrxn⁰ = (-787 kJ) + (-566 kJ)
2C (graphite) + O2 → 2CO ΔHrxn⁰ = -1353 kJ
SAMPLE PROBLEM
Calculate the standard enthalpy of formation of acetylene (C2H2) from its
elements:
2C(graphite) + H2(g) C2H2(g)
SPONTANEOUS PROCESSES
GENERAL CHEMISTRY 2
COURSE OUTCOME 3
SPONTANEOUS
PROCESSES
A spontaneous reaction is a reaction that favors the
formation of products at the conditions under which the
reaction is occuring.

A non-spontaneous reaction is a reaction that does not

favor the formation of products at the given set of
conditions.

CHM02 63
ENTROPY
GENERAL CHEMISTRY 2
COURSE OUTCOME 3
ENTROPY, S
measure of how spread out or dispersed the energy of a system is among the
different possible ways that system can contain energy

• W – number of microstates
• k – Boltzman constant (1.38 x 10 -23 J/K)
MICROSTATES AND
ENTROPY
A system with fewer microstates
(smaller W) among which to spread
its energy (small dispersal) has a
lower entropy.
A system with more microstates
(larger W) among which to spread its
energy (large dispersal) has a higher
entropy.

Microstates = specific wat in which

we arrange the energy of the system
SECOND LAW OF
THERMODYNAMICS

The entropy of the universe increases in a spontaneous process and remains

unchanged in an equilibrium process
GIBBS FREE ENERGY, G
Free Energy refers to the energy available to do work.
Spontaneous Reactions produce free energy as they proceed.

G = H – TS
where H is enthalpy, T is temperature, and S is entropy.
GIBB’S FREE ENERGY

ΔH ΔS ΔG
negative positive always negative
negative at higher temperatures, positive
positive positive
at lower temperatures
negative at lower temperatures, positive
negative negative
at higher temperatures
positive negative always positive
GIBBS FREE ENERGY, G

CHM02 74
SAMPLE PROBLEM
Calculate the standard free-energy changes of the reaction at 25°C.
SAMPLE PROBLEM
BOARD WORK
1. A 30.14-g stainless ball bearing at 117.82 °C is placed in constant-
pressure calorimeter containing 120.0 mL of water at 18.44 °C. If the
specific heat of the ball bearing is 0.474 J/g °C, calculate the final
temperature of the water. Assume that the calorimeter has negligible heat
capacity.
BOARD WORK
2. Calculate the heat of decomposition for this process at constant pressure
and 25°C:

CaCO3(s) → CaO(s) + CO2(g)

BOARD WORK
3. Calculate the heat of combustion for the following reaction from the standard
enthalpies of formation listed in appendix 3.

(a) C2H4(g) + 3O2(g) → 2CO2(g) 1 2H2O(l)

3. Find the enthalpy change for the reaction

CS2(l) + 3 O2(g) → CO2(g) + 2 SO2(g)
when:
C(s) + O2(g) → CO2(g); ΔHf = -393.5 kJ/mol
S(s) + O2(g) → SO2(g); ΔHf = -296.8 kJ/mol
C(s) + 2 S(s) → CS2(l); ΔHf = 87.9 kJ/mol
BOARD WORK