CHEM 26

Institute of Chemistry
University of the Philippines Diliman

Review of
01
Thermodynamics
Mae Criste D. Fajiculay
Chem 26 Introduction to Quantitative Chemical Analysis
Midyear AY 2022-2023
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Copyright
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• Note that the course pack provided to you in any form is intended
only for your use in connection with the course that you are
enrolled in. It is not for distribution or sale.
• Permission should be obtained from your instructor for any use
other than for what it is intended.

2
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General Outline
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This module aims to recall and enhance your knowledge on the

topics that are first taught in Chem 16 and are relevant to Chem 26.
These topics include:
• Solution Thermodynamics
• Ways of Expressing Concentrations
• Stoichiometric Calculations
• Gravimetric and Volumetric Analysis
Spotcheck questions and practice exercises are given to apply your
knowledge and hone your skills.

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Solution Thermodynamics
Internal Energy ٠ Enthalpy ٠ Entropy ٠ Gibbs' Free Energy
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Internal Energy (U)

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• Internal Energy, denoted as U, refers to the total energy in a system.

• This encompasses the energy associated to the following:
• Translational motion
• Molecular rotation
• Molecular vibration
• Intermolecular attraction
• Electron

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
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Internal Energy vs. Heat vs. Work

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• A system only contains internal energy. None of this energy is in the

form of heat and work on its own.
• When the system interacts with surroundings, it exchanges energy
through the means of heat and work. Thus, heat and work is only
present if there will be change in the energy of the system.

ILLUSTRATION
Think of a known online payment platform (e.g. GCash, PayPal). The amount you cash into
your account is all that you have. When you make an online transaction, say buying a bag
from a seller, then there will be a change in your account balance.
In this illustration, your cash is similar to the internal energy. It's all that you have on your own. The online
transaction is similar to heat and work. Through this, you are exchanging your cash with a seller, similar to
a system exchanging energy with its surroundings. Lastly, that online transaction is manifested in the
change in your cash, similar to heat and work manifested in the change in internal energy.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
6
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First Law of Thermodynamics

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• In gist, heat and work exist during a change in the internal energy
of a system. The relationship of these three variables is governed by
the first of law of thermodynamics
U = q + w (1)

where ΔU is change in internal energy (J), q is heat (J), and w is

work (J).
• It is equally practical to remember as well that work is a function of
change in volume, i.e. w = -PΔV.
• Therefore, if a system does not interact with its surroundings, or so-
called isolated, then ΔU = 0.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
7
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Heats of Reaction
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• Consider a reaction that goes from one state

(Ui) to another (Uf) as shown. In the first case,
the reaction was done at constant volume. In
the second one, it was done at constant
pressure.
• For the first case, the reaction was done at
constant volume. Since the system neither Figure 1. Illustration of two
expands nor contracts, then work is equal to states with equal ΔU but
zero. Eq. 1 then becomes ΔU = qv (or heat at done in different paths.
Adapted from Petrucci, et.al.
constant volume). (2011).

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
8
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Heats of Reaction
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• For the second case, the reaction was done at

constant pressure. This implies that work
cannot be equal to zero. The resulting
equation for the change in internal energy is
same with that of Eq. 1, only that the
variables are qualified based on the reaction
condition, i.e. q = qp (or heat at constant
pressure. Figure 1. Illustration of two
states with equal ΔU but
• This case is often the condition when we done in different paths.
Adapted from Petrucci, et.al.
conduct our experiments in the laboratory, (2011).
because we live under the constant pressure
of atmosphere.
Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
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Enthalpy (H)
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• Eqs. 2 and 3 represent the two cases we discussed previously. Eq. 2

is substituted to Eq. 3, since ΔU is the same for both cases.
U = qV (2)

U = q P + w (3)

qV = q P + w (4)

• The last step is to express the resulting equation (Eq. 4) in terms of

state functions. While qV and w can be expressed as ΔU and -PΔV
respectively, we need to introduce a new function for qP－enthalpy
(H).
H = U + PV (5)

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
10
Solutions.
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Change in Enthalpy (ΔH)

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• Eq. 5 gives rise to the well-known thermodynamic variable: change

in enthalpy, denoted as ΔH.
• It is more common to express the heat of a reaction as ΔH than ΔU.
• One reason is the condition where the reaction is done. As mentioned
earlier, we often perform our experiments under constant pressure.
• Another explanation is simplicity. We are often focused on knowing the
overall heat associated in the reaction, rather than distinguishing the
contributions of qP and w.

ILLUSTRATION
Think of electric bill. It shows not just the amount that corresponds to your
consumption but also the taxes that you are paying. This is important for the
call of accountability, but for a consumer like you, you just want to know how
much you are going to pay in total. In the same way, ΔH is more common
because it gives us the overall picture.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
11
Solutions.
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Standard Enthalpy of Reaction (ΔH°)

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• Standard enthalpy of reaction, denoted as ΔH°, refers to the change

in enthalpy associated in a reaction where all reactants and
products are in their standard states.
• The standard state of a pure substance is its state at a pressure of 1
bar and a particular temperature.
• It is IUPAC who recommends this value for Products

standard pressure.

Energy
ΔH°
• While temperature is strictly not part of the
definition, most tabulated values are compiled Reactants
at 298.15 K. Figure 2. Sample energy diagram
that illustrates ΔH°.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
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Features of ΔH°
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• Because enthalpy is a state function, various features of ΔH° can be

drawn and are now useful in calculating the heats of different
reactions.

1. ΔH°, along its sign, corresponds to a particular heat flow.

2. ΔH° is dependent on the amount of substances in the system.
3. ΔH° can be indirectly calculated through series of reactions.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
13
Solutions.
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Features of ΔH°
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1. ΔH°, along its sign, corresponds to a particular heat flow.

• If we look back on Figure 2, the enthalpy of the products is higher
than the reactants. For the reactants to be converted to products, it
needs to absorb heat from the surroundings. In this case, the
reaction is described as endothermic.
• For a more concrete example, consider the formation of nitrogen
oxide as shown. The reaction is endothermic, as seen from its
positive ΔH°. This implies that the reaction between nitrogen and
oxygen for them to produce nitrogen oxide.
N2(g) + O2(g) → 2 NO(g) ΔH° = 180.50 kJ (6)

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
14
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Features of ΔH°
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1. ΔH°, along its sign, corresponds to a particular heat flow.

• The reverse is also possible: the enthalpy of the products could be
lower than the reactants. For the reactants to be converted to
products, it needs to release heat to the surroundings. In this case,
the reaction is described as exothermic.
• The reverse of Eq. 6 can be the example. Since it was clear from the
previous slide that NO has a higher enthalpy than N2 and O2, then
the reverse reaction would involve liberation of heat. As seen, ΔH°
becomes negative.
2 NO(g) → N2(g) + O2(g) ΔH° = -180.50 kJ (7)

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
15
Solutions.
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Features of ΔH°
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1. ΔH°, along its sign, corresponds to a particular heat flow.

• As shown in those examples, the sign of ΔH° indicates whether heat
is absorbed or released by the system. If the process is reversed,
then the sign of ΔH° would also change.
• To reiterate,
(+) ΔH° = heat absorption = endothermic
(-) ΔH° = heat release = exothermic

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
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Features of ΔH°
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2. ΔH° is dependent on the amount of substances in the system.

• Consider this reaction again. The amount of heat absorbed by the
system corresponds to the production of two moles of NO. If the
production is reduced to one mole of NO, then the amount
absorbed is also reduced.
N2(g) + O2(g) → 2 NO(g) ΔH° = 180.50 kJ (6)

1/2 N2(g) + 1/2 O2(g) → NO(g) ΔH° = 90.25 kJ (8)

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
17
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Features of ΔH°
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3. ΔH° can be indirectly calculated through series of reactions.

• Consider a new reaction: 1/2 mole of N2 reacts with 1 mole of O2 to
produce 1 mole of NO2. How can we determine its ΔH°?
• We then can look on how this reaction goes. This conversion can be
described in two steps (Eqs. 9 and 10). When these two steps are
added up, we get our desired overall reaction (Eq. 11).
1/2 N2(g) + O2(g) → NO(g) + 1/2 O2(g) ΔH°= +90.25 kJ (9)

NO(g) + 1/2O2(g) → NO2(g) ΔH°= -57.07 kJ (10)

1/2 N2(g) + O2(g) → NO2(g) ΔH°= +33.18 kJ (11)

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
18
Solutions.
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Features of ΔH°
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3. ΔH° can be indirectly calculated through series of reactions.

• This property of ΔH° is governed by Hess' Law, which states that “If
a process occurs in stages or steps (even if only hypothetically), the
enthalpy change for the overall process is the sum of the enthalpy
changes for the individual steps.”

ILLUSTRATION
There's a lot of ways to get to Main Library from Institute of
Chemistry. You can combine different streets and turns but the
overall process is the same－from IC to Main Lib. In the same way,
we can add up different reaction steps and the sum of their
changes in enthalpy will correspond to that of the overall reaction.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
19
Solutions.
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A good start.
Reward yourself a break.
Remote learning is never easy. Spare some five minutes
to stretch out a bit and hydrate. Just make sure you'll be back.
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Standard Enthalpy of Formation (ΔHf°)

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• Standard enthalpy of formation, denoted as ΔHf°, refers to the

change in enthalpy associated in the formation of a substance from
the reference form of its elements, all in their standard states.
• To understand this, we need to reiterate how to write the formation
reaction for a particular substance.
• The substance of interest becomes the product.
• Look at the elements present in the chemical formula of the product. The
reference forms of these elements become the reactants.
• Account proper stoichiometry so that the reaction produces one mole of
the product. If this would lead to some non-integral coefficients, it's fine.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
21
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Standard Enthalpy of Formation (ΔHf°)

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• Apply those steps to write the formation reaction of NO.

• The product is NO.
• The elements are nitrogen and oxygen. Their reference forms are N2 and
O2, respectively.
• To produce one mole of NO, only 1/2 mole each of N2 and O2 are needed.
1/2 N2(g) + 1/2 O2(g) → NO(g) (12)

• Apply for HNO3 as well.

• The product is HNO3. The elements are hydrogen, carbon, and oxygen.
Their reference forms are H2(g), N2(g), and O2, respectively.
1/2 H2(g) + 1/2 N2(g) + 3/2 O2(g) → HNO3(aq) (13)

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
22
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Standard Enthalpy of Formation (ΔHf°)

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• The reference form of the elements is, in general, their most stable
forms at 1 bar and the indicated temperature (e.g. 298.15 K), which
we consider as conditions for standard state, too.
• The ΔHf° of a pure element in its reference form is equal to zero.
• Appendix D of General Chemistry by Petrucci, et.al. (2011) provides
a comprehensive table of the standard enthalpies of formation of
different compounds.
• The tables are arranged according to the elements.
• You can see that some forms have ΔHf° = 0. This implies that these are the
reference forms of a particular element.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
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Table 1. An excerpt of thermodynamic properties (ΔHf°, ΔGf°, S°, Cp) tabulated in Appendix DPhilippines
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General Chemistry by Petrucci, et.al. (2011). In this excerpt, it shows that Al(s) is the reference
form for aluminum because its ΔHf° is 0.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
24
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Table 2. A compilation of the reference forms of some common elements. Adapted from
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Petrucci, et.al. (2011). All these substances have standard enthalpies of formation equal to zero.

Element Reference Form

Bromine Br2(l)
Carbon C(graphite)
Chlorine Cl2(g)
Fluorine F2(g)
Hydrogen H+(aq) , H2(g)
Iodine I2(s)
Nitrogen N2(g)
Oxygen O2(g)
Phosphorus P(α white)
Sulfur S(rhombic)

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
25
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Spotcheck
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• Write down the formation reaction for NaHCO3(s).

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Calculating Heats of Reaction from ΔHf°

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• The conversion of reactants to products

involves two general steps. The reactants
decompose first to its reference forms, then
recombine to form the products.
• Consider the general reaction
2 NaHCO3(s) → Na2CO3(s) + CO2(g) + H2O(l) (14)

• NaHCO3 decomposes first to Na(s), H2(g),

C(graphite), and O2(g), which are the reference
Figure 3. An enthalpy
forms of elements in NaHCO3. These then diagram for decomposition
recombine to form the products, which are of NaHCO3 to products.
Na2CO3(s), CO2(g), H2O(l). Adapted from Petrucci et.al.
(2011).
Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
27
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Calculating Heats of Reaction from ΔHf°

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• From previous definition, the “decomposition”

in Fig. 3 is the inverse of the formation reaction
of the reactant (NaHCO3) while the
“recombination” is the formation reaction of the
products (Na2CO3, CO2, H2O).
• An equation can be roughly established to
calculate ΔH° for the overall.
ΔH°overall = (-ΔH°f,reactant) + (ΔH°f,product)
Figure 3. An enthalpy
diagram for decomposition
of NaHCO3 to products.
Adapted from Petrucci et.al.
(2011).
Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
28
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Calculating Heats of Reaction from ΔHf°

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• Thus, for a general reaction, the standard change in enthalpy

(ΔH°rxn) can be calculated from the standard enthalpies of
formation (ΔH°f) of the products and reactants as shown,

H rxn =  v p H f , p −  vr H f ,r (15)

where ΔH°rxn is the change in enthalpy for the reaction (J mol-1),

vp is the stoichiometric coefficient of product(s),
ΔH°f,p is the enthalpy of formation of product(s) (J mol-1),
vr is the stoichiometric coefficient of reactant(s), and,
ΔH°f,r is the enthalpy of formation of reactant(s) (J mol-1).

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
29
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Calculating Heats of Reaction from ΔHf°

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2 NaHCO3(s) → Na2CO3(s) + CO2(g) + H2O(l) (13)


H rxn =  v p H f , p −  vr H f ,r (15)

( )(
 mol Na2CO3 H f , Na2CO3  )
 

( 
H rxn = + molCO2 H f ,CO2 )( ) ( 
 − mol NaHCO3 H f , NaHCO3 )( ) (16)
 
( 
)(
+ mol H 2O H f , H 2O  )
  kJ  
 (1mol ) − 1131  
  mol  
  kJ     kJ 
H rxn = + (1mol ) − 393.5   − (2mol ) − 950.8
 kJ
 = 91.3 (17)
  mol     mol  mol
  kJ 
+ (1mol ) − 285.8 
  mol 

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
30
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Spotcheck
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• What kind of reaction is being represented in Fig. 3, endothermic or

exothermic? Use Eq. 15 to support your answer.

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If ΣΔH°f,r < ΣΔH°f,p , If ΣΔH°f,r > ΣΔH°f,p ,

then ΔH°rxn > 0. then ΔH°rxn < 0.

Figure 4. General illustration of Equation 14 applied on endothermic and exothermic reaction.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
32
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Practice
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• Calculate the standard enthalpy of the Table 3. Standard enthalpies of

formation of some substances.
following reactions. Use net ionic Adapted from Petrucci et.al. (2011).
equations. Substance ΔH°f (kJ mol-1)
• Precipitation of calcium carbonate from its Ca2+(aq) -542.8
dissolved ions CaCO3(s) -1207
• Dissolution of magnesium hydroxide to its CO32-(aq) -677.1
corresponding ions
H2O(g) -241.8
• Neutralization between a strong acid and a
H2O(l) -285.8
strong base
Mg2+(aq) -466.9
Mg(OH)2(s) -924.5
OH-(aq) -230.0

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Practice
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• Calculate the standard enthalpy of the Table 3. Standard enthalpies of

formation of some substances.
following reactions. Use net ionic Adapted from Petrucci et.al. (2011).
equations. Substance ΔH°f (kJ mol-1)
• Precipitation of calcium carbonate from its Ca2+(aq) -542.8
dissolved ions (Answer: +12.9 kJ mol-1) CaCO3(s) -1207
• Dissolution of magnesium hydroxide to its CO32-(aq) -677.1
corresponding ions (Answer: -2.4 kJ mol-1)
H2O(g) -241.8
• Neutralization between a strong acid and a
H2O(l) -285.8
strong base (Answer: -55.8 kJ mol-1)
Mg2+(aq) -466.9
Mg(OH)2(s) -924.5
OH-(aq) -230.0

34
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You've been so diligent.

Reward yourself a break.
Remote learning is never easy. Spare some five minutes
to stretch out a bit and hydrate. Just make sure you'll be back.
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Spontaneity
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• If a process is spontaneous, then it proceeds on its own without the

need for external action or intervention. Conversely, if a process is
nonspontaneous, then it will not occur unless an external action is
applied.
• If a process is spontaneous, then the reverse is nonspontaneous.
• Both spontaneous and nonspontaneous processes are possible, but
only spontaneous ones will occur without intervention.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
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Entropy (S)
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• Entropy, denoted as variable S, is the thermodynamic property that

is related to the distribution of a system's energy among the
available microscopic energy levels.
• It implies that a system with a fixed total energy (also constant
pressure and temperature) tends to spread out over an expanded
volume because there are more levels in which the molecules can
be redistributed.
ILLUSTRATION
Think of spraying perfume. At first, the perfume vapor is
concentrated in just one point, usually the origin of spray.
However, the vapor naturally expands to occupy the entire room.
This expansion happens even if the room is at constant pressure
and temperature. Thus, this process is best explained by entropy.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
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Figure 5. Three processes that show increase in entropy: (a) melting of solid, (b) evaporation of
liquid, (c) dissolution of solute in a solvent. For the last process, it is true for nonelectrolye
solutions, where ion-dipole forces do not exist.
Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
38
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 CHEM 26
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Chemistry

Change in Entropy (ΔS)

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• Fig. 5 shows that for these processes, the entropy of the final state
than the initial state. Since entropy is also a state function like
internal energy and enthalpy, then we can describe the process
using change in entropy (ΔS).
• Four situations generally lead to increase in entropy (ΔS>0).
• Solids are converted to liquids (or liquid solutions).
• Solids or liquids are converted to gases.
• The number of gaseous molecules increases due to a chemical reaction.
• Temperature of substance increases.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
39
Solutions.
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Chemistry

Evaluating Entropy Changes

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• Change in entropy is related to the amount of heat involved in the

process and temperature. This relationship is shown as
q
 S = (18)
T
where ΔS is change in entropy (J mol-1 K-1), q is heat (J mol-1), and T
is temperature (K).

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
40
Solutions.
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Chemistry

Evaluating Entropy Changes

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• For a phase transition, Eq. 18 becomes

H tr
S tr = (19)
Ttr
where ΔHtr is change in enthalpy for a phase transition.
• The superscript could be specified for a particular phase transition.
• “fus” : fusion, melting
• “vap” : vaporization

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
41
Solutions.
 CHEM 26
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Chemistry

Evaluating Entropy Changes

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University of the Philippines Diliman

• Consider the melting of ice to water. The change in entropy can be

calculated as shown.
H2O(s, 1 atm) ↔ H2O(l, 1 atm) ΔH°fus = 6.02 kJ (at 273.15 K) (20)

H tr
S fus = (21)
Ttr
6.02 kJ mol kJ
S fus = = 22.0 (22)
273.15K mol −1 K −1

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
42
Solutions.
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Chemistry

Third Law of Thermodynamics

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• The third law of thermodynamics states that “the entropy of a pure

perfect crystal at 0 K is zero.”
• This implies that there exists a condition in which the substance is
at its lowest possible energy state, or so-called zero-point energy.
The entropy at this point is zero.
• This principle gives rise to establishing absolute values of entropy
of substances. It also makes calculating the change in entropy for a
reaction possible.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
43
Solutions.
 CHEM 26
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Chemistry

Change in Entropy (ΔS°)

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• The standard change in entropy (ΔS°rxn) can be calculated from the

standard molar entropies (S°) of the products and reactants as
shown,

S rxn =  v p S p −  vr S r (23)

where ΔS°rxn is the change in entropy of the reaction (J mol-1 K-1),

vp is the stoichiometric coefficient of product(s),
S°p is the standard molar entropy of product(s) (J mol-1 K-1),
vr is the stoichiometric coefficient of reactant(s), and,
S°r is the standard molar entropy of reactant(s) (J mol-1 K-1).

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
44
Solutions.
 CHEM 26
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Chemistry

Change in Entropy (ΔS°)

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• By looking at Eq. 23, it shows that a positive ΔS° implies that a

reaction proceeds from a state of lower entropy (i.e. molecules of
reactants are more compact) to a state of higher entropy (i.e.
molecule of products more disordered).
• In gist,
(+) ΔS° = getting more disordered
(-) ΔS° = getting less disordered

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
45
Solutions.
 CHEM 26
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Chemistry

Practice
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• Calculate the change in entropy for the Table 4. Standard molar entropies
of formation of some substances.
decomposition of NaHCO3 to products Adapted from Petrucci et.al. (2011).
(Eq. 13) using Eq. 23. The calculation is Substance S° (J mol-1 K-1)
similar with Eqs. 15-17. CO2(g) 213.7
H2O(g) 188.8
H2O(l) 69.91
Na2CO3(s) 135.0
NaHCO3(s) 101.7

46
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Practice
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University of the Philippines Diliman

• Calculate the change in entropy for the Table 4. Standard molar entropies
of formation of some substances.
decomposition of NaHCO3 to products Adapted from Petrucci et.al. (2011).
(Eq. 13) using Eq. 23. The calculation is Substance S° (J mol-1 K-1)
similar with Eqs. 15-17. CO2(g) 213.7
(Answer: 215.2 J K-1) H2O(g) 188.8
H2O(l) 69.91
Na2CO3(s) 135.0
NaHCO3(s) 101.7

47
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Gibbs Free Energy (G)

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University of the Philippines Diliman

• Both heat flow and disorder are important in predicting the

spontaneity of a process.
• This gives rise to a new thermodynamic property that relates
enthalpy and entropy－Gibbs Free Energy, denoted as variable G.
• Gibbs free energy is also a state function, then the spontaneity of a
process can be evaluated in terms of the change in Gibbs free
energy (ΔG).

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
48
Solutions.
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Chemistry

Criteria for Spontaneity

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University of the Philippines Diliman

• The spontaneity of a reaction is dictated by the relationship of the

three mentioned state functions as shown,
G = H − TS (24)

where ΔG is the change in Gibbs free energy (kJ mol-1)

ΔH is the change in enthalpy (kJ mol-1)
ΔS is the change in entropy (J mol-1 K-1)
T is the temperature of that reaction (K).

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
49
Solutions.
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Criteria for Spontaneity

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University of the Philippines Diliman

• The value of change in Gibbs free energy calculated from Eq. 24

reflects the spontaneity of a reaction.
(-) ΔG = spontaneous
(+) ΔG = non-spontaneous
• If there is no change, that is ΔG = 0, then the process is at
equilibrium.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
50
Solutions.
 CHEM 26
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Spotcheck
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• Will a reaction that is exothermic and leads to increased disorder be

spontaneous?

51
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Table 5. Criteria for spontaneous change using Gibbs free energy.

ΔH ΔS ΔG Result Example
2 NO2(g) → 2 N2(g) +
(−) (+) (−) Spontaneous at all temperatures
O2(g)
(−) Spontaneous at low temperatures
(−) (−) H2O(l) → H2O(s)
(+) Non-spontaneous at high temperatures
(+) Non-spontaneous at low temp
(+) (+) 2 NH3(g) → N2(g) + 3 H2(g)
(−) Spontaneous at high temperatures

(+) (−) (+) Non-spontaneous at all temperatures 3 O2(g) → 2 O3(g)

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
52
Solutions.
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Standard Free Energy Change (ΔG°)

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University of the Philippines Diliman

• The standard free energy change for a reaction can be calculated in

two ways. One is using Eq. 24, provided that these values are
calculated at standard states, that is using ΔH°rxn and ΔS°rxn.
• The second way is using the standard free energy change for the
formation of a substance (ΔGf°), highly similar to Eqs. 15 and 23.

Grxn =  v p G f , p −  vr G f ,r (24)

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
53
Solutions.
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Chemistry

Non-standard Conditions
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• So far, we've been dealing with thermodynamic properties,

particularly Gibbs free energy, with species at their standard states.
• If under non-standard conditions, spontaneity can still be predicted
using the following relationship

Grxn = Grxn + RT ln Q (25)

where ΔGrxn is the non-standard free energy change (kJ mol-1),

ΔG°rxn is the standard free energy (kJ mol-1),
R is the thermodynamic gas constant (8.3145 J mol-1 K-1),
T is the temperature, and
Q is the reaction quotient.
Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
54
Solutions.
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Non-standard Conditions
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• In Eq. 25, we introduced reaction quotient (Q). Reaction quotient

refers to the ratio of the amount of products to that of reactants,
raised to their stoichiometric coefficients.
• For a hypothetical reaction aA → cC, it is expressed as
PCc C c
Q= a = a (25)
PA A
• As seen, the amounts can be expressed as partial pressures for
gaseous species (PX) or concentrations ([X]) for aqueous species.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
55
Solutions.
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Equilibrium Constant (Keq)

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University of the Philippines Diliman

• If the free energy change for a reaction is zero, then the reaction is
at equilibrium. Thus, the reaction quotient becomes the equilibrium
constant (Keq).

Grxn = Grxn + RT ln Q (25)

0 = Grxn + RT ln Q (26)

Grxn = − RT ln K eq (27)

• We will discuss equilibrium constant further in the next lessons.

Petrucci R., Hering F., Madura J. and Bissonette C. (2011). General Chemistry: Principles and Modern Applications, 10th ed.; Boston, MA: Pearson Learning
56
Solutions.
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Short Quiz
The short quiz is available through UVLe.
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You've made it to the end!

Congratulations!
This is the end of the lesson.