SCI 401 General Chemistry: ©2021 Batangas State University

SCI 401
GENERAL CHEMISTRY
1
©2021 Batangas State University
Matter and Energy :Energy
Changes in Chemical
Reactions
● HEAT CAPACITY AND CALORIMETRY
● ENTHALPY
● SPONTANEITY
● ENTROPY
● LAWS OF THERMODYNAMICS
2 ©2021 Batangas State University
Heat Capacity and Calorimetry
All chemical reactions exhibits the two
fundamental laws: the law of conservation of
mass and the law of conservation of energy.
Energy, is defined as the capacity to do

work. Energy, unlike matter, cannot be seen,
touched, smelled, or weighed but all of its
form are capable of doing work.

Chemists define work as directed energy change resulting from
a process.
There are different forms of energy namely:
● Kinetic energy
● Thermal energy
● Chemical energy, and
● Potential energy
Note: All forms of energy can be transformed from one form

4
to another, but can neither be created nor destroyed.
Law of conservation of energy: the total quantity of
energy in the universe is assumed constant.
Heat is the transfer of thermal energy between two bodies

that are at different temperatures
Thermochemistry is the study of heat change in chemical

reactions.
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SYSTEM is the specific part of the universe that is of interest to us
, while SURROUNDINGS are the rest of the universe outside the
system.
Three types of system: (a) Open, (b) Closed and (c) Isolated system.
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Heat Capacity and Calorimerty
An open system can exchange mass and

energy, usually in the form of heat with its
surroundings.
Example. Boiling soup in an open saucepan on

a stove.
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A closed system allows the transfer of energy

(heat) but not mass.
Example. A pressure cooker on a stove with its

lid tightly closed and the whistle in position
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An isolated system does not allow the transfer

of either mass or energy.
Example. A thermos flask containing hot water
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The combustion of hydrogen gas in oxygen is a

chemical reaction that releases considerable
amount of energy.
2H2(g) + O2(g) 2H2O(l) + energy
Any energy lost from the system, or the given
reacting mixture, is gained by the surroundings.
Thus, combustion reactions is an exothermic
process, which is any process that gives off heat.
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Considering another reaction, such as
decomposition of mercury (II) oxide (HgO)
at high temperatures:
energy + 2HgO(s) 2Hg(l) + O2(g)
This is an example of endothermic

process, in which heat has to be supplied to
the system by the surroundings.
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Calorimetry is the measurement of heat changes.
Calorimeter is a closed container designed specifically to

measure heat changes.
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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 (J/g·°C).
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 (J/°C.).
Note: Specific heat is an intensive property whereas heat capacity is an

extensive property. The relationship between the heat capacity and
specific heat of a substance is C = ms,where m is the mass of the
substance in grams.
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Heat (q) is a path function, which values are dependent on the

path taken. With specific heat and the amount of a substance,
change in the temperature (Δt ) predicts the amount of heat (q)
absorbed or released in a particular process. The equations for
calculating the heat change are given by
q = CΔt or q = msΔt
t -t
where Δt = final initial
Note: +q is for endothermic process and -q is for exothermic

process.
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Heat of combustion is usually measured by placing a known mass of a compound in a
steel container called a constant-volume bomb calorimeter, which is filled with oxygen at
about 30 atm of pressure.
The closed bomb is immersed in a known amount of water and the sample is ignited
electrically, and the heat produced by the combustion reaction can be calculated accurately
by recording the rise in temperature of the water.
The heat given off by the sample is absorbed by the water and the bomb.
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Because no heat enters or leaves the system throughout the process, the heat change
of the system (qsystem) must be zero and we can write
qsystem = qcal + qrxn
qsystem = 0
where qcal and qrxn are the heat changes for the calorimeter and
the reaction, respectively. Thus,
q = -q
rxn cal
To determine qcal, we need to know the heat capacity of the

calorimeter (Ccal) and the temperature rise
qcal = CΔt
The quantity of Ccal is calibrated by burning a substance with an
accurately known heat of combustion.
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There is a simpler device that the constant-volume calorimeter and that is
constant-pressure calorimeter, which is used to determine the heat changes for
non-combustion reactions. They used it in measuring the heat effects of a variety of
reactions such as acid-base neutralization as well as Heat of solution and heat of
dilution. The heat changes for the process (qrxn) is equal to the enthalpy change (ΔH).
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Example 2.2: A lead (Pb) pellet having a mass of 26.47 grams at 89.98oC was
placed in a constant-pressure calorimeter of negligible heat capacity containing
100.0mL of water. The water temperature rose from 22.50oC. What is the specific
heat of the lead pellet?
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Practice Problem 2.3: A 30.14 grams stainless steel ball bearing at 117.82oC is placed in a
constant-pressure calorimeter containing 120.0mL of water at 18.44oC. if the specific heat of
the ball bearing is 0.474 J/g oC, Calculate the final temperature of the water. Assume the
calorimeter to have negligible heat capacity.
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Changes in Chemical
Reactions
● ENTHALPY
● SPONTANEITY
● ENTROPY
Enthalpy
Enthalpy is a thermodynamic quantity equivalent to the total

heat content of a system. It is equal to the internal energy of the
system plus the product of pressure and volume.
The reaction is considered as expansion when there is a net
increase in the number of moles of a gas after the reaction and
conversely, it is compression if more gas molecules are consumed
than are produced.
The work is done on the surroundings for an expansion process
and it is done on the system for a compression process. There is no
work done if there is no net change in the number of moles of gases
from the reactants to products.
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Enthalpy
The expansion of a gas against a constant external pressure (such as

atmospheric pressure). The gas is in a cylinder fitted with a weightless
28 movable piston.
Enthalpy
In general, for a constant-pressure process we write
ΔE = q + w
= qp - PΔV
where subscript “p” means constant-pressure condition
qp = ΔE + PΔV
Therefore, Enthalpy (H) is defined by the equation

H =E + PV
where E is the internal energy of the system and P and V are the pressure
and volume of the system, respectively. Enthalpy, pressure, energy and
volume are all state functions, that is, the changes depend only on the initial
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state and final state.
Enthalpy
Energy is a state function. Using potential energy as an example, we find that the net increase in
gravitational potential energy when we go from the same starting point to the top of a mountain is
always the same, regardless of how we get there.
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Enthalpy
For any process, the change in enthalpy according is given by

ΔH =ΔE + Δ(PV)
If the pressure is held constant, then
ΔH =ΔE + PΔV
The two quantities, ΔE and ΔH, can be associated with a reaction.
If the reactions occurs under constant-volume conditions, then the
heat change (qv) is equal to ΔE. On the other hand, when the reaction is
carried out as constant-pressure, the heat change (qp) is equal to ΔH
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Enthalpy
For any reaction of the type, We can equate the heat change into the change in
enthalpy.
Reactants Products
From the reaction, we can compute for the enthalpy of reaction, ΔH, as the
difference between the enthalpies of the products and the enthalpies of the reactants.
The enthalpy of reaction can be positive or negative, depending on the process.
● Endothermic process (heat absorbed by the system from the surroundings), ΔH is
positive (that is, ΔH > 0).
● Exothermic process (heat released by the system to the surroundings), ΔH is
negative (that is, ΔH < 0).
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Enthalpy
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Enthalpy
It is important to remember that the ΔH value does not refer to a

particular reactant or product. It simply means that the quoted ΔH value
refers to all the reacting species in molar quantities. Thus, the following
conversion factors can be created:
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Enthalpy
Thermochemical equations shows the enthalpy change as well as the

mass relationships. It is essential to specify a balanced equation when
quoting the enthalpy change of a reaction.
Helpful guidelines in writing and interpreting thermochemical equations.

● Stoichiometric coefficients always refer to the number of moles of a
substance
H2O (s) H2O (l) ΔH = 6.01 kJ/mol
● If you reverse a reaction, the sign of ΔH changes
H2O (l) H2O (s) ΔH = -6.01 kJ/mol
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Enthalpy
● If you multiply both sides of the equation by a factor n, then ΔH must

change by the same factor, n.
2H2O (s) 2H2O (l) ΔH = 2 x 6.01 kJ/mol = 12.0 kJ/mol
● The physical states of all reactants and products must be specified in

thermochemical equations
H2O (s) H2O (l) ΔH = 6.01 kJ/mol
H2O (l) H2O (g) ΔH = 44.0 kJ/mol
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Enthalpy
37
Enthalpy
38
Changes in Chemical
Reactions
● ENTHALPY
● SPONTANEITY
● ENTROPY
Spontaneity
Thermodynamics deals with the interconversion of heat
and other forms of energy. Studying thermodynamics will
enable us to determine whether or not a reaction will
occur when reactants are brought together under a specific
conditions example temperature, pressure and
concentration.
If a reaction does occur under the given
set of conditions is called spontaneous
reaction. However, if a reaction does not
occur under specified conditions, it is said
to be nonspontaneous.
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Spontaeneity
Exothermicity favors the spontaneity of a reaction but does not

guarantee it. Just as it is possible for an endothermic reaction to be
spontaneous, it is possible for an exothermic reaction to be
nonspontaneous.
In other words, we cannot decide whether or not a chemical reaction
will occur spontaneously solely on the basis of energy changes in the
system. To make this kind of prediction we need another thermodynamic
quantity, which turns out to be entropy.
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Changes in Chemical
Reactions
● ENTHALPY
● SPONTANEITY
● ENTROPY
Entropy
To determine the spontaneity of the reaction, a

thermodynamic quantity called entropy must be
considered.
Entropy (S) is described as a measure of how spread
out or dispersed the energy of a system is among the
different possible ways that system can contain
energy.
The greater the randomness, the greater the entropy.
Most processes are accompanied by a change in
entropy.
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Entropy
In 1868 Boltzmann showed that the entropy of a system is related to the
natural log of the number of microstates (W):
S = k(lnW)
where k is called the Boltzmann constant (1.38 x 10-23 J/K). Thus, the larger
the W, the greater is the entropy of the system. And entropy as a state function,
it can be measured as,
ΔS = Sf – Si
where Si and Sf are the entropies of the system in the initial and final states,
respectively.
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Entropy
Or can be translated to,

ΔS = k(lnWf) – k(lnWi)
= kln(𝑊𝑓 / 𝑊𝑖)
where Wi and Wf are the

corresponding numbers of microstates in
the initial and final state. Thus, if Wf .
Wi, ΔS > 0 and the entropy of the system
increase.
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Entropy
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Entropy
Standard entropy is the absolute entropy of a substance at 1 atm and

25°C. (Recall that the standard state refers only to 1 atm. The reason for
specifying 25°C is that many processes are carried out at room
temperature.) The units of entropy are J/K or J/K·mol for 1 mole of the
substance.
Entropies of elements and compounds are all positive (that is, S° >0).
For different substances in the same phase, molecular complexity

determines which ones have higher entropies.
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Entropy
For example diamond and graphite are solids, but diamond has a more
ordered structure and hence a smaller number of microstates.
Consider the natural gases methane and ethane. Ethane has a more
complex structure and hence more ways to execute molecular motions,
which also increase its microstates.
Both helium and neon are monatomic gases, which cannot execute
rotational or vibrational motions, but neon has a greater standard entropy
than helium because its molar mass is greater.
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Entropy
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Entropy
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Changes in Chemical
Reactions
● ENTHALPY
● SPONTANEITY
● ENTROPY
Law of Thermodynamics
The First Law of Thermodynamics states that

energy can be converted from one form to another,
but it cannot be created or destroyed.
One measure of these changes is the amount of

heat given off or absorbed by a system during a
constant-pressure process, which chemists define as a
change in enthalpy (ΔH).
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The Second Law of Thermodynamics is defined as
the entropy of the universe increases in a spontaneous
process and remains unchanged in an equilibrium
process.
Spontaneous process: ΔSuniv = ΔSsys + ΔSsurr > 0

Equilibrium process: ΔSuniv = ΔSsys + ΔSsurr = 0
The second law of thermodynamics tells us that a

spontaneous reaction increases the entropy of the
universe; that is, ΔSuniv > 0.
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In order to determine the sign of ΔSuniv for a

reaction, however, we would need to calculate both
ΔSsys and ΔSsurr. In general, we are usually concerned
only with what happens in a particular system.
We know that for a spontaneous process, we have
ΔSuniv = ΔSsys + ΔSsurr > 0

ΔSuniv = ΔSsys - (ΔHsys / T) > 0
TΔSuniv = -ΔHsys +TΔSsys > 0
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Now we have a criterion for a spontaneous reaction that

is expressed only in terms of the properties of the system
(ΔHsys and ΔSsys) and we can ignore the surroundings
-TΔSuniv = ΔHsys - TΔSsys < 0
This equation says that for a process carried out at

constant pressure and temperature T, if the changes in
enthalpy and entropy of the system are such that ΔHsys -
TΔSsys is less than zero, the process must be spontaneous.
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In order to express the spontaneity of a reaction more directly, we introduce
another thermodynamic function called Gibbs† free energy (G), or simply free
energy:
G = H – TS
All quantities pertain to the system, and T is the temperature of the system.
You can see that G has units of energy. Like H and S, G is a state function.
The change in free energy (ΔG) of a system for a constant-temperature
process is
ΔG = ΔH – TΔS
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The standard free-energy of reaction (ΔGo) is the free-energy change for a
reaction when it occurs under standard-state conditions.
The Third Law of thermodynamics states that entropy of a perfect

crystalline substance is zero at the absolute zero of temperature.
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Supplementary Videos
Heat Capacity and Calorimetry :
https://youtu.be/yhNHJ7WdT8A
Thermochemistry and Enthalpy :

https://youtu.be/ZVhJ4TO8a-M
https://youtu.be/2q2u5sj4V00
Laws of Thermodynamics, Entropy, and Gibbs Free Energy:

https://youtu.be/8N1BxHgsoOw
60

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SCI 401

Energy, is defined as the capacity to do

3 ©2021 Batangas State University

Note: All forms of energy can be transformed from one form

Heat is the transfer of thermal energy between two bodies

Thermochemistry is the study of heat change in chemical

An open system can exchange mass and

Example. Boiling soup in an open saucepan on

A closed system allows the transfer of energy

Example. A pressure cooker on a stove with its

An isolated system does not allow the transfer

Example. A thermos flask containing hot water

The combustion of hydrogen gas in oxygen is a

energy + 2HgO(s) 2Hg(l) + O2(g)

This is an example of endothermic

Calorimetry is the measurement of heat changes.

Calorimeter is a closed container designed specifically to

specific heat (s) of a substance is the amount of heat

heat capacity (C) of a substance is the amount of heat

Note: Specific heat is an intensive property whereas heat capacity is an

Heat (q) is a path function, which values are dependent on the

Note: +q is for endothermic process and -q is for exothermic

To determine qcal, we need to know the heat capacity of the

Enthalpy is a thermodynamic quantity equivalent to the total

The expansion of a gas against a constant external pressure (such as

Therefore, Enthalpy (H) is defined by the equation

For any process, the change in enthalpy according is given by

It is important to remember that the ΔH value does not refer to a

Thermochemical equations shows the enthalpy change as well as the

Helpful guidelines in writing and interpreting thermochemical equations.

● If you multiply both sides of the equation by a factor n, then ΔH must

2H2O (s) 2H2O (l) ΔH = 2 x 6.01 kJ/mol = 12.0 kJ/mol

● The physical states of all reactants and products must be specified in

H2O (l) H2O (g) ΔH = 44.0 kJ/mol

Exothermicity favors the spontaneity of a reaction but does not

To determine the spontaneity of the reaction, a

Or can be translated to,

where Wi and Wf are the

Standard entropy is the absolute entropy of a substance at 1 atm and

For different substances in the same phase, molecular complexity

The First Law of Thermodynamics states that

One measure of these changes is the amount of

Spontaneous process: ΔSuniv = ΔSsys + ΔSsurr > 0

The second law of thermodynamics tells us that a

In order to determine the sign of ΔSuniv for a

We know that for a spontaneous process, we have

ΔSuniv = ΔSsys + ΔSsurr > 0

Now we have a criterion for a spontaneous reaction that

-TΔSuniv = ΔHsys - TΔSsys < 0

This equation says that for a process carried out at

The Third Law of thermodynamics states that entropy of a perfect

Thermochemistry and Enthalpy :

Laws of Thermodynamics, Entropy, and Gibbs Free Energy:

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