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MBMB 1212: General Chemistry

Chapter 5

Chemical Reactions and Acid - Base Concepts

September – December 2022

Enthalpy
In chapter 1, we saw that electrons achieve a lower energy state
when they occupy a bonding molecular orbital. It stands to reason,
then, that breaking a bond requires an input of energy

For a bond to break, the electrons

in the bonding MO must receive
energy from their surroundings.
Specifically, the surrounding
molecules must transfer some of
their kinetic energy to the system
(the bond being broken). The term The change in enthalpy (ΔH) for
enthalpy is used to measure this any process is defined as the
exchange of energy: exchange of kinetic energy, also
called heat (q), between a
system and its surroundings
∆𝐻 = 𝑞 (𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒) under conditions of constant
pressure
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Enthalpy
• Breaking a bond requires energy
• Bonds can break homolytically or heterolytically:

How does the body deal with free radicals?

• Bond dissociation energy (BDE) or ΔH for bond breaking generally

represents the energy associated
with HOMOLYTIC cleavage

Bond Dissociation Energies

kJ/MOL KCAL/MOL kJ/MOL KCAL/MOL

Bonds to H C–C bonds
435 104 368 88
435 104 356 85
410 98 351 84
569 136 293 70
431 103 234 56
368 88 381 91
297 71
498 119 159 38
242 58

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Bond Dissociation Energies

How is heat energy exchanged between the reaction (system) and
the solution (surroundings) for each scenario below?
i. H• and F• free radicals come together to form bonds

ii. A C–Br bond is broken

iii. A strong bond is broken and a weak bond is formed

iv. A weak bond is broken and a strong bond is formed

Enthalpy, ΔH of a reaction
• Match the reaction coordinate diagrams below with the
following statements:
– The reaction causes the surrounding temperature to
DECREASE
– The reaction causes the surrounding temperature to
INCREASE

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Entropy, ΔS
• The sign of ΔH° is not the ultimate measure of whether or not a
reaction can or will occur. Although exothermic reactions are
common, there are still plenty of examples of endothermic
reactions that readily occur.
• This begs the question: What is the ultimate measure for
determining whether or not a reaction can occur? The answer to
this question is entropy, which is the underlying principle guiding
all physical, chemical, and biological processes.
• Entropy is informally defined as the measure of disorder,
randomness, or freedom associated with a system, although this
definition is overly simplistic

Entropy, ΔS
• If the energy of molecules can be distributed in a higher
number of vibrational, rotational, and translational
states, the sample will have a greater entropy

• Molecules exhibit vibrational, rotational, and

translational motion

• Which of the two molecules below should have greater

entropy? WHY?

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Molecular motions

Entropy, ΔS
• Consider the ENTROPY and ENTHALPY change for
the following process:

• The number of possible translational

distributions for the molecules increases with
increasing volume

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Entropy, ΔS
• A process that involves an increase in entropy is said to be
spontaneous. That is, the process can and will occur, given
enough time. Chemical reactions are no exception, although the
considerations are slightly more complex than in a simple free
expansion
• In the case of free expansion, we only had to consider the change
in entropy of the system (of the gas particles). The surroundings
were unaffected by the free expansion. However, in a chemical
reaction, the surroundings are affected. We must take into
account not only the change in entropy of the system but also the
change in entropy of the surroundings:

∆𝑆𝑡𝑜𝑡 = ∆𝑆𝑠𝑦𝑠 + ∆𝑆𝑠𝑢𝑟𝑟

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Entropy, ΔS
Two ways in which the entropy of a chemical system can
increase

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Gibbs Free Energy, ΔG

• We have seen that that entropy is the one and only criterion that
determines whether or not a chemical reaction will be
spontaneous. But it is not enough to consider ΔS of the system
alone; we must also take into account ΔS of the surroundings:

∆𝑆𝑡𝑜𝑡 = ∆𝑆𝑠𝑦𝑠 + ∆𝑆𝑠𝑢𝑟𝑟

• The total change in entropy (system plus surroundings) must be
positive in order for the process to be spontaneous

• It is certainly not possible to observe the entire universe, so how

can we possibly measure ΔSsurr? Fortunately, there is a clever
solution to this problem

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Gibbs Free Energy, ΔG

∆𝐻𝑠𝑦𝑠
∆𝑆𝑠𝑢𝑟𝑟 =
𝑇
• ΔSsurr is now defined in terms of the system. Both ΔHsys and T
(temperature in Kelvin) are easily measured, which means that
ΔSsurr can in fact be measured.
• Plugging this expression for ΔSsurr into the equation for ΔStot, we
arrive at a new equation for ΔStot for which all terms are
measurable:

∆𝐻𝑠𝑦𝑠
∆𝑆𝑡𝑜𝑡 = − + ∆𝑆𝑠𝑦𝑠
𝑇

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Gibbs Free Energy, ΔG

• This expression is still the ultimate criterion for spontaneity
(ΔStot must be positive). As a final step, we multiply the entire
equation by -T, which gives us a new term, called Gibbs free
energy:

−𝑇∆𝑆𝑡𝑜𝑡 = ∆𝐻𝑠𝑦𝑠 + 𝑇∆𝑆𝑠𝑦𝑠

∆𝐺

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Gibbs Free Energy, ΔG

In other words, ΔG is a repackaged way of expressing total entropy:

−∆𝐺 = ∆𝐻 + 𝑇∆𝑆

Associated with the

Associated with the
change in entropy of
change in entropy of
the surroundings
the system

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Gibbs Free Energy, ΔG

• If a process at a given
temperature is calculated
to have a negative ΔG, the
process is EXERGONIC
– It will be SPONTANEOUS and
favor the products
– Note that G is plotted rather
than H
• Does the value for ΔG tell
us about the rate of the
reaction?
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Gibbs Free Energy, ΔG

• If a process at a given
temperature is calculated
to have a (+) ΔG, the
process is ENDERGONIC
– It will be
NONSPONTANEOUS
and favor the reactants
– What does it mean
exactly to FAVOR the
reactants?

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Equilibrium
• Consider an EXERGONIC
process with a negative ΔG.
Will every molecule of A and B
be converted into products?
• No. An equilibrium will
eventually be reached in
which all four compounds are
present
– A spontaneous process will
simply favor the products
meaning there will be more
products than reactants

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Equilibrium

• In any reaction, collisions are necessary

• As [A] and [B] decrease, collisions between A and B will
occur less often
• As [C] and [D] increase, collisions between C and D will
occur more often
– The more often C and D collide, the more often
collisions will occur with enough free energy for the
reverse reaction to take place
• EQUILIBRIUM is dynamic and occurs when the forward
and reverse reaction rates are equal

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Equilibrium

Equilibrium is also the

state with the lowest
free energy overall

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Equilibrium

• An equilibrium constant (Keq) is used to show the

degree to which a reaction is product or reactant
favored:

– Keq, ΔG, ΔH, and ΔS are thermodynamic terms. They

do not describe reaction kinetics. What is the
difference?

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Equilibrium
• What trends do you notice in Table 6.2 below?

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Kinetics
• Recall that a (-) sign for ΔG tells us a process is
product favored (spontaneous)
– That does NOT tell us anything about the RATE or
KINETICS for the process
• Some spontaneous processes are FAST, such as
explosions

• Some spontaneous processes are SLOW, such as

C (diamond)  C (graphite)

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Kinetics
• The rate of a reaction tells us how many
molecules are reacting in a given period of time
– Give some examples for typical reaction rate units

• For reactions to take place, reactants must

collide with sufficient force. WHY?

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Kinetics
• The reaction rate (the number of collisions that
will result in product production in a given
period of time) is affected by multiple factors:
1.The concentrations of the reactants
2.The activation energy
3.The temperature
4.Geometry and sterics
5.The presence of a catalyst
• How will an increase in [reactant] generally
affect the reaction rate?
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Kinetics – Rate Law Equations

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Kinetics – Factors that Affect Rates

• Locate the activation

energy in the Figure

• Why must the free energy

(G) increase before the
products can be formed?

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Kinetics – Factors that Affect Rates

1. A lower Eact result in a greater reaction rate?

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Kinetics – Factors that Affect Rates

2. An increase in temperature increases the rate
of reaction?

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Kinetics – Factors that Affect Rates

3. Geometry and sterics
4. Presence of a catalyst

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Acids & Bases

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Acids and Bases

• Brønsted-Lowry definitions:
– Acids donate a proton
– Bases accept a proton

example:

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Conjugate Acids and Bases

• Brønsted-Lowry definitions:
– A conjugate acid results when a base accepts a
proton
– Recall :

• Label the acid, base, and the conjugates in the reaction

below

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Lewis Acids and Bases

• Lewis acid/base definition:
– A Lewis acid accepts a pair of
electrons
– A Lewis base donates a pair of
electrons
Gilbert Newton Lewis
• Explain how this reaction fits both (1875-1946)

definitions

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Lewis Acids and Bases

• Some Lewis acid/base reactions cannot be classified
using the Brønsted-Lowry definition
• Explain how this reaction fits the Lewis definition but
not the Brønsted-Lowry definition

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Hybridization in BF3

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Lewis Acids and Bases

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Acid-Base Chemistry
REACTIONS OF WATER:
- Reversible self-dissociation = ionization

• Note hydrogen atoms do not exist as free H+ in solution

but as hydronium ions (H3O+). For simplicity, we just write
H+
• Use law of mass action to define the equilibrium point of
the dissociation reaction:

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Acid-Base Chemistry
• Keq for pure water determined experimentally to be 1.8 x
10-16 M at 25C
• Concentration of pure H2O = 55.5M (weight of water in 1 L
(1000 g) divided by mw of 18)

• Defined pH as the negative logarithm of the hydrogen ion

concentration:

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Acid-Base Chemistry

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Measuring pH
• Indicators
– Phenophthalein, phenol red,
bromothymol blue
pH > 7.5
• pH Paper pH = 6.0-7.5
pH < 6.0

• pH Meters

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Practice Problems
• What is the H+ concentration of a solution with pH of 3.82?

• What is the pH of a solution that has an H+ concentration

of 1.75 x 10-5 mol/L?

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Dissociation of an Acid

Conjugate base

• Acetic acid/acetate pair:

• Equilibrium constant for the dissociation of the acid (Ka)

• Smaller pKa = Stronger acid

• Larger pKa = Weaker acid (stronger base)
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• Strong acids
— Ionize completely
in H2O
— HCl and HNO3

• Weak acids
— Not completely
dissociated in
water, so [H+] will
be much lower
that [HA]
—Phosphoric, acetic
Lactic and carbonic
acids
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Exercise

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