These examples show that processes that occur spontaneously in one direction

cannot, under the same conditions, also take place spontaneously in the opposite direction.

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Experience tells us that ice melts spontaneously above 0°C even though the process is

endothermic. In this case, the assumption that spontaneous processes always decrease a

system’s energy fails. 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.

Entropy

We have to introduce a new thermodynamic quantity called entropy to determine the

spontaneity of the reaction. 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. A cup of hot water has a certain amount of entropy due

to the dispersal of energy among the various energy states of the water molecules (for

example, energy states associated with the translational, rotational, and vibrational motions

of the water molecules). If left standing on a table, the water loses heat to the cooler

surroundings. Consequently, the entropy of the system increases because closely spaced

energy levels leads to a greater dispersal among the energy levels.

In 1868 Boltzmann showed that the entropy of a system is related to the natural log

of the number of microstates (W):

S = klnW
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. Entropy is a state function and the change can be

measured as:

ΔS = Sf – Si

where Si and Sf are the entropies of the system in the initial and final states,

respectively.

ΔS = klnWf – klnWi

= kln9$

9%

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 increases.

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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. We use joules rather than kilojoules because entropy values are

typically quite small. 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. Both diamond and graphite are solids, but diamond has a more

ordered structure and hence a smaller number of microstates. Therefore, diamond has a
smaller standard entropy than graphite. Consider the natural gases methane and ethane.

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SCI 401 –GENERAL CHEMISTRY

Ethane has a more complex structure and hence more ways to execute molecular motions,

which also increase its microstates. Therefore, ethane has a greater standard entropy than

methane. 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. Heavier atoms have more closely spaced energy levels so there is a greater

distribution of the atoms’ energy among the levels. Consequently, there are more microstates

associated with these atoms.

Example 4

Predict whether the entropy change is greater or less than zero for each of

the following processes: (a) freezing ethanol, (b) evaporating a beaker of

liquid bromine at room temperature, (c) dissolving glucose in water, (d)

cooling nitrogen gas from 80°C to 20°C.

Strategy To determine the entropy change in each case, we examine

whether the number of microstates of the system increases or

decreases. The sign of ΔS will be positive if there is an increase in

the number of microstates and negative if the number of

microstates decreases.

Solution (a) Upon freezing, the ethanol molecules are held rigid in position.

This phase transition reduces the number of microstates and

therefore the entropy decreases; that is, ΔS < 0.

(b) Evaporating bromine increases the number of microstates

because the Br2 molecules can occupy many more positions in

(c) Glucose is a nonelectrolyte. The solution process leads to a

greater dispersal of matter due to the mixing of glucose and

water molecules so we expect ΔS > 0.

(d) The cooling process decreases various molecular motions.

This leads to a decrease in microstates and so ΔS < 0.

Practice Exercise 4

How does the entropy of a system change for each of the following

processes? (a) condensing water vapor, (b) forming sucrose crystals from a

supersaturated solution, (c) heating hydrogen gas from 60°C to 80°C, and (d)

subliming dry ice.

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4.0 Laws 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).

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.

The second law of thermodynamics tells us that a spontaneous reaction increases the

entropy of the universe; that is, ΔSuniv > 0. 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. Therefore, we need another

thermodynamic function to help us determine whether a reaction will occur spontaneously

We know that for a spontaneous process, we have

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.

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.

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 (both H and TS are in energy units). 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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SCI 401 –GENERAL CHEMISTRY

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.

Calculate the standard free-energy changes for the following reactions at

25°C.

(a) CH4(g) + 2O2(g) à CO2(g) + 2H2O(l)

(b) 2MgO(s) à 2Mg(s) + O2(g)

Strategy To calculate the standard free-energy change of a reaction, we

look up the standard free energies of formation of reactants and

products. Note that all the stoichiometric coefficients have no units

so ΔG°rxn is expressed in units of kJ/mol, and ΔG°f for O2 is zero

because it is the stable allotropic element at 1 atm and 25°C.

Solution

(a) ΔG°rxn = [ΔG°f(CO2) + 2ΔG°f(H2O)] - [ΔG°f(CH4) + 2ΔG°f(O2)]

=[(-394.4 kJ/mol) + (2)(-237.2 kJ/mol)] - [(-50.8 kJ/mol) + (2)(0

kJ/mol)]

=-818.0 kJ/mol

(b) ΔG°rxn = [2ΔG°f(Mg) + ΔG°f(O2)] - [2ΔG°f(MgO)]

=[(2kJ/mol) + (0 kJ/mol)] - [ (2)(-569.6kJ/mol)]

=1139 kJ/mol

Practice Exercise 5

Calculate the standard free-energy changes for the following reactions at

25°C:

(a) H2(g) + Br2(l) à 2HBr(g)

(b) 2C2H6(g) + 7O2(g) à 4CO2(g) + 6H2O(l)

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ASSESSMENT TASK
1. Define the following terms:

a) Thermodynamics

b) Isolated system

c) Spontaneous

d) Enthalpy

e) Entropy

2. On what law is the first law of thermodynamics based? Explain the sign

conventions in the equation ΔE = q + w.

3. Explain what is meant by a state function. Give two examples of quantities that

are state functions and two that are not.

4. What is the difference between specifi c heat and heat capacity? What are the

units for these two quantities? Which is the intensive property and which is the

extensive property?

5. A sheet of gold weighing 10.0 g and at a temperature of 18.0°C is placed flat on a

sheet of iron weighing 20.0 g and at a temperature of 55.6°C. What is the final

temperature of the combined metals? Assume that no heat is lost to the

surroundings. (Hint: The heat gained by the gold must be equal to the heat lost

by the iron.)

6. State whether the sign of the entropy change expected for each of the following

processes will be positive or negative, and explain your predictions.

a) PCl3(l) + Cl2(g) à PCl5(s)

b) 2HgO(s) à 2Hg(l) + O2(g)

c) H2(g) à 2H(g)

d) U(s) + 3F2(g) à UF6(s)

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SCI 401 –GENERAL CHEMISTRY

Chang, R. and Goldsby, K. A. (2017). Chemistry, (12th International Edition), New York:

McGraw-Hill.

Brown, L., Brown, L. S., & Holme, T. (2011). Chemistry for engineering students. Nelson

Education.

Fahlman, B. D., Purvis-Roberts, K. L., Kirk, J. S., Bentley, A. K., Daubenmire, P. L., Ellis, J. P., &

Mury, M. T. (2018). Chemistry in Context: Applying Chemistry to Society (No. 540

C517cc). McGraw-Hill.

Silberberg, M. (2012). Principles of general chemistry. McGraw-Hill Education.

https://chem.libretexts.org/