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Chemical Equilibrium
Chemical Equilibrium
CHEMICAL EQUILIBRIUM
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Outline
V. Chemical Equilibrium
•Insight into Concrete Production and Weathering
•Chemical Equilibrium
•Equilibrium Constants
•Equilibrium Concentrations
•LeChaterlier’s Principle
•Solubility Equilibria
•Free Energy and Chemical Equilibrium
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Learning Outcomes
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Concrete Production and Weathering
• Uses of admixtures
• Water reducers: lower the amount of water in the concrete
without affecting the ability to work with it.
• Air entraining admixtures: improve concrete durability by
stabilizing small air bubbles within the cement portion of
concrete, particularly when exposed to freeze-thaw cycles.
• Waterproofers: combat effects of moisture.
• Accelerators or retardants: affect the speed of the hardening
process.
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Concrete Production and Weathering
• Accelerators or
retardants: affect the
speed of the
hardening process.
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Concrete Production and Weathering
• Weathering of concrete
• Freeze-thaw cycles
• Aging of concrete through carbonation, where CO2 from the air
diffuses into the concrete.
This photo sequence shows the water level in two glasses over the
course of 17 days. The glass on the left is covered.
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Forward and Reverse Reactions
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Forward and Reverse Reactions
• A chemical system reaches equilibrium when the rate of the forward reaction
equals the rate of the reverse reaction.
• The concentration of products and reactants does not change at equilibrium.
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Mathematical Relationships
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Mathematical Relationships
• or
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The Equilibrium (Mass Action) Expression
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Example Problem 1:
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Example Problem 1:
SOLUTION:
aA + bB ⇄ cC
2A + B ⇄ 2C
2SO2 + O2 ⇄ 2SO3
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Gas Phase Equilibria: KP vs. KC
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Gas Phase Equilibria: KP vs. KC
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Homogeneous and Heterogeneous Equilibria
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Homogeneous and Heterogeneous Equilibria
• For the decomposition reaction of CaCO3(s) forming CaO(s) and CO2(g), the
equilibrium constant only depends on the CO2 concentration because CaCO3 and
CaO are solids.
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Example Problem 2:
SOLUTION:
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Numerical Importance of the Equilibrium Expression
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Example Problem 3:
PROBLEM: In Example Problem 2, we saw that hydroxide ions precipitate with
calcium. Magnesium ions show similar behavior. The two pertinent
equilibria are
SOLUTION: Both equilibrium constants are much greater than one, but the
value for the reaction with magnesium ions is significantly larger
than that for calcium. Thus magnesium hydroxide has a much
greater tendency to form and will be the more likely product.
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Mathematical Manipulation of Equilibrium Constants
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Adjusting the Stoichiometry of the Chemical Reaction
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Example Problem 4:
SOLUTION:
(a) the reaction as written
(c) the reaction as written but with all coefficients in the equation halved
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Equilibrium Constants for a Series of Reactions
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Example Problem 5:
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Example Problem 5:
SOLUTION:
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Units and the Equilibrium Constant
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Equilibrium Concentrations
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Equilibrium Concentrations
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Example Problem 6:
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Example Problem 6:
• The concentration of HI =
0 initially, so the reaction
will shift to the right to
achieve equilibrium.
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Example Problem 6:
SOLUTION:
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Example Problem 6:
SOLUTION:
[HI] = 2x
[HI] = 2(0.040)
[HI] = 0.080M
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Example Problem 7:
PROBLEM: The equilibrium constant for the reaction of chlorine gas with
phosphorus trichloride to form phosphorus pentachloride is 33 at
250°C. If an experiment is initiated with concentrations of 0.050 M
PCl3 and 0.015 M Cl2, what are the equilibrium concentrations
of all three gases?
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Example Problem 7:
SOLUTION:
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Example Problem 7:
SOLUTION:
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Example Problem 7:
SOLUTION:
[Cl2] = 0.015 – x
[Cl2] = 0.015 – 0.0088
[Cl2] = 0.006M
[PCl3] = 0.050 – x
[PCl3] = 0.050 – 0.0088
[PCl3] = 0.041M
[PCl5] = x
[PCl5] = 0.0088M
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Mathematical Techniques for Equilibrium Calculations
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Le Châtelier’s Principle
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Effect of a Change in Concentration
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Effect of a Change in Concentration
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Effect of a Change in Concentration
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Effect of a Change in Concentration
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Effect of a Change in Concentration
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Example Problem 8:
PROBLEM: Acetic acid, CH3COOH, has the peculiar property of being a
retarding agent for concrete at low concentration and an
accelerator at high concentrations. A solution of acetic acid in
equilibrium with hydrogen ions and acetate ion, CH3COO-, can
be disturbed in several ways. Predict the change in the reaction
quotient, Q, when
(a) sodium acetate is added to the system,
(b) additional acetic acid is added to the system, and
(c) sodium hydroxide is added to the system. Then use those
predictions to explain how the equilibrium shifts in response to
each stress.
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Example Problem 8:
SOLUTION: The equilibrium is
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Example Problem 8:
SOLUTION: The equilibrium is
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Example Problem 8:
SOLUTION: (c) Sodium hydroxide is added. Again the sodium ion does not
play a significant role in this perturbation, and at first
glance, it might seem like the hydroxide ion doesn’t either.
But if we use a little bit of the chemical intuition you’ve
developed by this point in the course, we should realize that
OH- and H+ ions will react with one another to form water.
This will decrease the concentration of H+. Because the
concentration of a product is reduced, the size of the
numerator decreases, making Q < K. Thus the equilibrium
shifts to form more products.
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Effect of a Change in Pressure
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Effect of a Change in Pressure
• For the equilibrium between NO2 and N2O4, the increase in pressure is offset
by reducing the moles of gas present by forming N2O4.
• Decreasing the volume to 2 L initially increases the pressure to 5.0 atm.
• Equilibrium is re-established when the pressure is reduced to 4.6 atm by
reacting 2 NO2 to form N2O4.
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Example Problem 9:
PROBLEM: HCN is an important but potentially dangerous industrial chemical.
It can be produced in several ways, including by the reactions
shown below. Assuming that each system is initially at equilibrium,
predict the direction in which the reaction will go to respond to the
indicated stress.
(b) ;
pressure is decreased
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Example Problem 9:
There are two moles of gas on the left and four moles of gas on
the right. If pressure is increased, the equilibrium will move to the
left.
(b) ;
pressure is decreased
There are seven moles of gas on the left and eight moles of gas
on the right. Decreasing pressure favors the reaction that produces
more moles of gas, so the reaction to the right is favored.
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Effect of a Change in Temperature on Equilibrium
• Increase the temperature, equilibrium shifts away from the side with
the heat.
• Decrease the temperature, equilibrium shifts toward the side with
the heat.
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Effect of a Change in Temperature on Equilibrium
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Effect of a Change in Temperature on Equilibrium
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Effect of a Change in Temperature on Equilibrium
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Free Energy and Chemical Equilibrium
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Graphical Perspective
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Free Energy and Nonstandard Conditions
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Example Problem 10:
PROBLEM: The conversion of methane gas (CH4) to methanol (CH3OH), which
is a liquid at room temperature, is an area in which considerable
research is being done. Still, this process is not yet economically
viable. Using tabulated thermodynamic data, calculate the
equilibrium constant for the following reaction at 25°C:
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Example Problem 10:
SOLUTION:
K = 1.73 x 1020
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Example Problem 10:
SOLUTION:
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Borates and Boric Acid
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Borates and Boric Acid
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REFERENCES
PRIMARY REFERENCE
L. S. Brown & T. A. Holme. Chemistry for Engineering Students.
OTHER REFERENCES
W.L. Masterton & C. N. Hurley. Chemistry :Principles and Reactions.
R. Chang. Chemistry.
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