EXPERIMENT 4:

CHEMICAL EQUILIBRIUM

JOSE, ESTELLE DIANE D. AND VERGARA, ANGELICA R.

THWX1
BS CHEMICAL ENGINEERING

CHEMICAL EQUILIBRIUM

Chemical Equilibrium speaks about the condition in which forward and reverse reaction rates of reversible
processes are equal. At this point, the concentrations of the reactants and products remain unchanged where the
ratio of the molar concentrations of the products over those of the reactant, raised to their corresponding
stoichiometric coefficients is also constant. And this ratio is known as the equilibrium constant of the reaction.

RESULTS AND DISCUSSION Since at equilibrium forward and backward

rates are equal:
Chemical equilibrium is a state where in the
chemical activities of the products and reactants have
no net change over time. This state does not mean
that the reaction has already stopped; nor does it and the ratio of the rate constants is also a constant,
mean that the quantities of the reactants and now known as an equilibrium constant.
products are equal but at this point, the
concentration of the reactants is equal to the
concentration of the products.

At equilibrium, the equilibrium constant, K,

can be determined. For any reaction such as,
to be at equilibrium the rates of the forward and
backward (reverse) reactions have to be equal.
In this chemical equation with arrows
pointing both ways to indicate equilibrium, A and B
are reactant chemical species, S and T are product
species, and α, β, σ, and τ are the stoichiometric
coefficients of the respective reactants and products.
The equilibrium position of a reaction is said to lie
far to the right if, at equilibrium, nearly all the
reactants are used up and far to the left if hardly any
product is formed from the reactants.
Moreover, equilibrium meets LeChatelier’s
Principle which explains the behavior of an
equilibrium system when changes to its reaction
conditions occur. If a dynamic equilibrium is
disturbed by changing the conditions, the position of
equilibrium moves to partially reverse the change.
For example, adding more product from the outside
will cause an excess of products, and the system will
try to counteract this by increasing the reverse
reaction and pushing the equilibrium point backward
(though the equilibrium constant will stay the same).
In this experiment, four equilibrium states
were analyzed: the equilibrium in copper and
ammonia system, the chromate and dichromate
system, the iron (III) chloride and thiocyanate system
and the Cobalt (II) ions system.

The effect of the concentration of the

different species in equilibrium and temperature was
also given a focus in this experiment.
where A, B, S and T are active masses and k+ and k−
are rate constants. A. COPPER-AMMONIA SYSTEM
 [Cu(H2O)4]2+ + 4NH3 ↔ [Cu(NH3)4]2+ + 4H2O
Initial color - light (pale) blue
Adding 6 drops of NH3 results a color
change, from a light to a dark one. This dark blue
product is [Cu(NH3)4]SO4 which is dark blue in
nature.
Then, by the time [Cu(NH3)4]SO4 is added
by 6 drops of HCl, the color of the solution turns to
its original color, light blue.
In order to retain equilibrium, the system
must proceed with the reverse reaction. As observed,
the solution changed its color from dark blue to pale
blue by addition of HCl, indicating that the reverse
reaction has undergone.
B. CHROMATE-DICHROMATE SYSTEM
2CrO42- + 2H+ ↔ Cr2O72- + H2O (acidic)
Cr2O72- + 2OH- ↔ 2CrO42- + H2O (basic)
Chromate – yellow; dichromate – orange
1. K2CrO4
Upon addition of H2SO4, the
solution turns to orange. While with the
addition of NaOH to K2CrO4, there is no
visible reaction.
When the H2SO4 is added to the
solution, it dissociated producing more H +
ions. While there is an increase in H+ ions,
the system proceed to forward reaction. The
system forms [Cr2O7]2- ions to retain
equilibrium. The orange color of the final
solution indicated that the forward reaction
proceeds.
And with NaOH, its addition
increase OH ions to the solution. Therefore,
the reaction is driven reverse in order to
retain equilibrium. The solution retains its
color since as the reaction proceeds to the
reverse, it also produces chromate ions.
2. K2Cr2O7
The solution retains its orange
color by addition of H2SO4. It turns yellow
by the time it mixes up with NaOH.
As more H+ ions are produced, the
reaction is driven backward. Therefore, the
solution showed no visible change and
remained its color.
There is an increase of OH in the
solution after adding NaOH, thus pushing
the reaction forward indicated by the change
of orange into yellow. As the reaction was
driven forward, more chromate ions were
formed. The yellow solution indicates the
presence of the chromate ions.
C. IRON (III) CHLORIDE – THIOCYANATE
SYSTEM
Fe3+ + SCN- ↔ [Fe(SCN)]2+
Initial Color – Light Orange
Upon addition of FeCl3, the solution’s color
evolves to a dark orange. As the FeCl3‘s
concentration increases, the shift in equilibrium is to
the right. The forward reaction proceeds to maintain
equilibrium producing more of the product.
Here with KSCN, the color of the solution
also changed to dark orange. The shift in equilibrium
for the solution is also to the right. As a reactant,
increasing its concentration has driven the reaction to
form more of the products.
As NaCl is added to the solution, it increases
the concentration of the Cl- which is on the product
side. As it increases, the system produces more
reactants to maintain equilibrium thus shifting to the
left. This is indicated by the changing of color to light
yellow orange.
ANSWERS TO QUESTION
1. Based on the principles of equilibrium,
explain the observations in Parts A and C.
What can you infer about the magnitude of
the equilibrium constants for these
reactions? What can you infer about the
signs of their ΔG?
For Part A:
[Cu(H2O)4]2+ + 4NH3 ↔ [Cu(NH3)4]2+ + 4H2O
The solution is initially CuSO 4 and
derives its pale blue color from the
[Cu(H2O)4]2+ ions.
 Based on the principles of Signs of ΔG
equilibrium, adding NH3 will shift the
reaction towards the forward direction in ∆G for both reactions is 0, since
order to attain a new equilibrium. This both are in equilibrium.
produces more [Cu(NH3)4]2+ ions, making
2. What was the effect of the acidity of the
the solution royal blue in color. When HCl
medium on the chromate and the dichromate
is added, it reacts with ammonia in the
ions in the solution?
solution to form ammonium chloride,
NH4Cl, which is soluble and colorless. This
The Chromate-Dichromate System
reduces the amount of NH3, shifting the
reaction in the reverse direction, producing Acidic Solution:
more [Cu(H2O)4]2+ ions, therefore making 2CrO42- + 2H+ ↔ Cr2O72- + H2O
the solution pale blue in color.

For Part C: Basic Solution:

Cr2O72- +2OH- ↔ 2CrO42- + H2O
Fe3+ + SCN- ↔ [Fe(SCN)]2+

The solution is initially light orange Based on the equations above, it

in color containing ferric, chloride and can be seen that the system in dynamic
thiocyanate ions. equilibrium will be sensitive to the acidity or
basicity of the solution. The dichromate ion
Adding FeCl3 shifts the reaction in is favored in acidic solution while the
chromate ion is favored in basic solution.
the forward direction since there is an
increase in both Fe3+ ions and chloride ions. 3. From the following reactions:
This forms more [Fe(SCN)]2+ ions making
the solution a darker shade of orange. The HCrO4- ↔ CrO42- + H+ K1 = 3.2x10-7
same goes with the addition of KSCN. 2HCrO4- ↔ Cr2O72- + H2O K2 = 37
H+ + OH- ↔ H2O Kw = 1.0x10-14
Adding NaCl, however, increases
only the chloride ions, creating an imbalance Derive the equilibrium constant expressions
in the ratio of ferric and chloride ions, more for:
chloride ions are present and lack ferric ion a. 2CrO42- + 2H+ ↔ Cr2O72- + H2O
counterparts.
2CrO42- + 2H+ ↔ 2HCrO4- (1/K1)2
To be able to relieve this
2HCrO4- ↔ Cr2O72- + H2O K2
imbalance, the complex is dissociated back
to Fe3+ and SCN- until the Fe3+ ions balance 2CrO4 + 2H ↔ Cr2O7 + H2O
2- + 2-
Ka
out the amount of Cl- added, a shift towards
Ka = (1/K1)2(K2) = (1/3.2x10-7)2(1.0x10-14)
the reverse direction occurs, the amount of
= 0.098
complex decreases thereby reducing the
orange color. Formation of FeCl4- ions,
b. Cr2O72- + 2OH- ↔ 2CrO42- + H2O
which are colorless, is favored

(given by the equation Fe3+ + 4Cl- ↔ Cr2O72- + H2O ↔ 2HCrO4- 1/K2

FeCl4-), further reducing the orange color of HCrO4 ↔ CrO4 + H
- 2- +
K12
the solution. H + OH ↔ H2O
+ -
K w2
Cr2O72- + 2OH- ↔ 2CrO42- + H2O Kb
Magnitude of K
Kb = (1/K2)(K1)2(Kw)2
 = (1/37)(3.2x10-7)2(1.0x10-14)2 not proceed favorably such that the
= 2.8x1043 amount of PO43- ions formed is too
4. The reaction below competes with the small to affect equilibrium. The color of
formation of the [Fe(H2O)5SCN]2+ complex: the solution will remain the same.

Fe3+(aq) + 4Cl-(aq) ↔ FeCl4-(aq) 5. Compare the values to Keq in each of the

Keq four conditions described in number 4.

Explain what will happen to the coor of a

a. Q>K
dilute solution containing FeCl4 if: b. Q<K
c. Q<K
a.) a solution containing Ag+ was added. d. Q=K
The solution will become more
yellow since the addition of AgCl will
react with the chloride ions present
forming solid AgCl, reducing the
amount of chloride ions and shifting
towards the reverse reaction. More
ferric ions are formed therefore making
the solutions more yellow.
REFERENCES

b.) NaCl solution was added [1] Petrucci, R.H., Harwood, W.S., Herring, F.G.
The solution will become a lighter General Chemistry: Principles and Modern
shade of yellow. The addition of NaCl Applications (8th ed.). Prentice-Hall, Inc., USA.
increases the amount of chloride ions 2002.
present, shifting towards the forward
reaction forming more FeCl4- ions. The [2] http.//en.wikipedia.com/chemical_equilibrium
ions formed are colorless therefore
turning the solution lighter yellow,
almost colorless compared to its initial
color.

c.) Concentrated HCl was added

The solution will turn colorless.
Adding concentrated HCl increases the
chloride ions indefinitely forming
significant amounts of FeCl4- ions
enough to make the solution completely
colorless. The concentrated HCl allows
the reaction to proceed completely in
the forward reaction due the the high
concentrations of chloride ions.

d.) Concentrated H3PO4

Addition of concentrated H3PO4
will not have any significant effect the
equilibrium condition. Since H3PO4 is a
weak acid, moreover, a concentrated
weak acid, dissociation of the acid will