Experiment 7

Chemical Thermodynamics
• The purpose of the experiment
• In this experiment you will examine how various stresses cause
equilibrium systems to shift (changing the concentration and
temperature.
• Explain your observations according to Le Chatelier’s principle
Introduction
Thermodynamic factor concerns about the stability of the reactants and products.
When the reaction reaches equilibrium, the reaction shifts towards the more stable
material (reactant or product). If the products are more stable, the products will be
predominant and have a higher concentration than the reactants. In this case, the
value of K (equilibrium constant) will be greater than 1. The reverse is true, If the
reactants are more stable, the reactants will be predominant and have a higher
concentration than the products. In this case, the value of K (equilibrium constant)
will be less than 1.
aA + bB cC + dD

c d K>1 [A]a [B]b < [C]c [D]d

K = [C] [D]
K<1 [A]a [B]b > [C]c [D]d
[A]a [B]b
Some chemical reactions are reversible; that means, not only do the reactants react to form
products, but the products can in turn reform into the original reactants. When a reversible
system reaches a point at which the rate of the forward reaction equals the rate of the reverse
reaction, the system is said to be at equilibrium.
At equilibrium, no observable changes in the system can be noted. It is important to understand
that at equilibrium all reaction participants are present, as well as all product particles.
If the concentration of one of the species in the equilibrium system changes, or if the temperature
changes, the equilibrium tends to shift in a way that compensates for the change.
LeChâtelier’s principle, proposed by Henri Louis LeChâtelier in 1888.
It states that if an external stress (change in concentration, temperature, etc.) is applied to a
system in a state of dynamic equilibrium, the equilibrium shifts in the direction that minimizes
the effect of that stress.
I. Changes in concentration:

• Changes in the concentrations of chemicals will shift chemical equilibrium

according to Le Chatelier’s Principle as such:
aA ⇄ bB
• When the concentration of a reactant is increased, the chemical equilibrium will
shift towards the products (right). More product is formed and the concentration
of the reactants decreases as the concentration of the products increases.
• When the concentration of a product increases, the chemical equilibrium will shift
towards the reactants (left). Less product is formed and the concentration of the
reactants increase as the concentration of the product decreases.
A- The Chromate-Dichromate Ion Equilibrium:
• The yellow chromate ion will react with the hydronium ion from an acid to form the orange
dichromate ion according to the following equation.
2CrO42-(aq) + 2H3O+(aq) ⇄ Cr2O72-(aq) + 3H2O(l)
yellow orange

• If a strong base (NaOH) is added to the system, it will react with hydronium ion on the left side of
equation;
H3O+(aq) + OH-(aq) ⇄ H2O(l)

• The acid removed from equilibria and so the reaction shift to relive the stress or disturbance caused
by its removal. As result the chromate ion is reformed.
Shift to left after adding OH

2 CrO42− (aq) +2 H3O+ (aq) Cr2O72− (aq) + 3 H3O

Yellow OH− Orange

3 H2O

• https://www.youtube.com/watch?time_continue=40&v=zP9qEiaL4kQ&feature=emb_logo
2 CrO42− (aq)
H3O+ Cr2O72− (aq)

Yellow
Orange

Shift to left after adding OH

2 CrO42− (aq)
OH− Cr2O72− (aq)

Yellow
Orange
b. The Metal-Ammonia Ion:

• Aqueous solution of copper ion appears sky blue. The color of the solution change
in the presence of added ammonia. Because the metal-ammonia bond is stronger
than the metal-water bond, ammonia substitution occurs and equilibrium shift right,
forming the metal ammonia ions.
Cu(H2O)42+ (aq) + 4NH3(aq) ⇄ Cu(NH3)4 2+ (aq) + 4H2O(l)
• If a strong acid H+, is added to the system, it will react with ammonia.
• The ammonia is removed from the equilibria and the reaction shift to the left to
relive the stress caused by its removal. As a result the aqueous Cu2+ solution is
reformed.
Cu(H2O)42+ (aq) + 4NH3(aq) ⇄ Cu(NH3)42+(aq) + 4H2O(l)
+ 4H+(aq)

4NH4+(aq Cu(H2O)42+ (aq)

NH3 (aq) Cu(NH3)42+ (aq)

sky blue
Dark blue

Cu(H2O)42+ (aq) H3O+ (aq) Cu(NH 3)42+ (aq)

sky blue
Dark blue

https://www.youtube.com/watch?v=00Lrkgf-qD4
C. Multiple Equilibria with Silver Ion:
C1. Silver Carbonate Equilibrium:

• When a precipitate forms in a solution, the solid is in equilibrium with the ions.
This can be illustrated with an equilibrium equation. For example, a saturated
solution of silver carbonate is described by
• Ag2CO3(s) ⇄ 2Ag+(aq) + CO32-(aq)
• The addition of nitric acid will dissolves silver carbonate. H+ ions react with the
carbonate ions on the right side of chemical reaction. The system shifts to the right
replace the carbonate ions. The Ag2CO3 dissolves, and carbonic acid, H2CO3,
forms
Ag2CO3(s) ⇄ 2Ag+(aq) + CO32-(aq)
+ 2H+(aq)

H2CO3(aq) ⇄ CO2(g) + H2O(l)

• Because carbonic acid is unstable at room temperature it decomposes to
water and carbon dioxide. The silver ion and nitrate ion (from HNO3)
remain in solution.
CO2 (g)

Ag2CO3 HNO 3 (aq)

••••• Ag+ (aq) + NO3−(aq)

••••
•
Ag2CO3 (s) Ag+ (aq) + CO3−2 (aq) solid dissolves
C.2. Silver Chloride Equilibrium:

• Addition of chloride ion (from HCl) to the solution which contains silver
and nitrate ions causes the formation of a silver chloride ( AgCl) precipitate.
This precipitate is now in equilibrium will its Ag+ and Cl- ions.
Ag+(aq)+ Cl-(aq) ⇄ AgCl(s)

• The addition of aqueous ammonia (NH3) removes the silver ion from the
equilibrium by forming the complex Ag(NH3)2+ , thus shifting the equilibrium
position to the left and causing AgCl to dissolve.
 Ag+(aq)+ Cl-(aq) ⇄ AgCl(s)
+ 2NH3(aq)

Ag(NH3)2+

2 NH3 (aq) 2 H+
− AgCl
Cl AgCl
[Ag(NH3)2]+ (aq)
Ag+ ••••• •••••
•••• ••••
• •

precipitate solid dissolves re-precipitate

https://www.youtube.com/watch?v=LM6y9maUL68
C.3.Silver Iodide Equilibrium:

• If the iodide ion, I- (from KI) is added to the equilibrium below, solid silver
iodide will formed

Ag+(aq)+ 2NH3(aq) ⇄ Ag(NH3)2+(aq)

I-(aq)

AgI(s)

• The iodide ion removes the silver from the system, causing a dissociation of the
Ag(NH3)2+ ion and a shift to the left.
II. The Effect of Concentration and Temperature on Equilibrium:

• To use Le Chatelier’s principle to describe the effect of a temperature change on a

system at equilibrium,

• For endothermic process,

• Treat energy as a reactant ,then the position equilibrium shift to right as
temperature increase and K value increase
• For exothermic process,
• Treat energy as a product ,then the position equilibrium shift to left as temperature
increase and K value decrease
• The effect of adding ion common to those already present in a system at a state of
equilibrium is called common ion effect. This effect is observed in this experiment
for the following equilibria:

Co(H2O)62+ (aq)+ 4Cl– (aq) ⇄ CoCl42– (aq) + 6 H2O(l) Endothermic

Pink Blue

• This equilibria is shifted by changes in the concentration of anions.

Adding the chloride ion will shift the reaction to the right and blue color forms.

Cl− (aq)
[Co(H2O)6]2+ (aq) + 4 Cl− [CoCl4]2− (aq)
heat

pink Dark blue

[Co(H2O)6]2+ (aq) + 4 Cl− [CoCl4]2− (aq) + 6 H2O
The effect of temperature on this system will also be examined.
Since the reaction is endothermic, the equilibrium will shift to the
right as temperature increases. CoCl42– is more stable at higher
temperatures.

https://www.youtube.com/watch?v=crr5ZMHCJ_Y
Thank you