Expt 9: Colligative Properties

Freezing Point Depression and Molar Mass Determination

Freezing point and freezing point

Objectives depression
• The freezing point of Naphthalene
and freezing point of a solution
containing a weighed amount of
sulfur and naphthalene was
determined.
• The molar mass of sulfur was
calculated based on the decrease of
the freezing point of the solution of
sulfur in naphthalene

Solutions
• are homogeneous mixtures of two
or more substances in a single
phase.
• In the classification of matter,
mixtures can either be homogenous
or heterogeneous.
• Homogeneous mixtures are referred
to as solutions.
• In a given solution, there are two
components:
1. Solvent – greater amount
2. Solute – lesser amount
colligative properties
• Are properties of solutions that are
dependent on their concentration,
not on the nature of the solute/
solid particles.
a) Freezing point depression
b) Boiling point elevation
c) Lowering of vapor pressure
d) Osmotic pressure
• Result from a lowering of the
chemical potential of the solvent in
the presence of a solute which is an
entropy effect.
• The freezing point (normally the
same as the melting point) is the
temperature at which the liquid
solvent and solid solvent are at
equilibrium, so that their vapor
pressures are equal.
• Freezing point depression is the
decrease of the freezing point of a
solvent on the addition of a non-
volatile solute.
➢ a phenomenon why adding a
solute to the solvent results to
a decrease in the freezing
point of the solvent!
• Freezing or becoming solid creates
order which in turn decreases entropy
when a non-volatile solute is added to
your solvent.
• Below is the phase diagram for water
in terms of the effect of solute on
boiling point and freezing point of
water.
• a Phase diagram is a map of
pressure versus temperature

• y-axis: pressure; x-axis: temperature
• the phase diagram shows the
temperatures and pressures at which
various phases (solid, liquid, gas) of
a substance can exist.
• the solid lines identify the
temperatures and pressures at which
an equilibrium exist between phases.
• called solid-liquid curve
➢ shows an equilibrium
between solid and liquid
• called liquid-vapor curve
➢ At a particular pressure and
temperature, it shows an
equilibrium between liquid
and vapor.
• called solid-gas curve
➢ At a particular pressure and
temperature, it shows an
equilibrium between solid and
gas.
• In these solid lines there are two
phases that are exist/ present.
• Green Lines- represent the pressure
and the temperature of a normal
boiling and freezing point of water.
• Purple Lines- represent pressure
and temperature of the boiling and
freezing point of the solution.
• At 1 atm, the normal boiling point of
water is 100 ° C which is presented
by no. 1 and the normal freezing point
is present by no. 2
• From 1-3, the temperature increases.
Meaning, the boiling point is elevated
from pure solvent to solution when a
solution is added to pure solvent.
• On the other hand, the freezing point
is lowered Which is represented by
numbers 2 and 4.
• The freezing point depression is the
difference between freezing point of
the pure solvent and that of the
solution.
• In a molecular level, if a pure solvent
freeze, its particles become more
ordered.
➢ From gas to liquid to solid, the
particles become more
ordered.
➢ Solid is more ordered than
liquid than gas and vice versa
(disordered).
Freezing point depression
∆Tf = Tf ° − Tf = K f m
• 𝑇𝑓 ° = freezing point of the pure solvent
• 𝑇𝑓 = freezing point of the solution
• 𝐾𝑓 = molal freezing point depression
constant, °C/m or °C kg/mol
• 𝑚 = molality of solution, mol/kg
experiment
• Determination of cooling curve of
pure naphthalene (C10H8)
o The naphthalene is a white
crystalline solid Without
characteristic odor (Strong
mothball odor)
• Determination of cooling curve of
naphthalene with known amount of
sulfur (S8)
• See figure below for the appendix of gas. Meaning, there are two
determination of cooling curve. phases present. Whatever is the
temperature of the horizontal line,
it corresponds to the boiling point
or the condensation temperature
of the substance.
• As liquid changes to solid, second
horizontal line, corresponds to the
freezing point or the melting point of the
substance.
• Before and after the horizontal line it
shows how the state changes from one
phase to another. So, there is a decrease
in temperature.
Tf (pure solvent)

Cooling curve

Tf (solution)

• Ideally the freezing point of the pure

solvent or the Naphthalene reaches a
plateau at its freezing point.
• A line graph that represents the • For the cooling curve, it does not reach a
change of phase of matter. Typically, plateau but decreases slowly the
from a gas to a solid or a liquid to a naphthalene or as the solvent gradually
solid. freezes.
• The independent variable (X-axis) is
time and the dependent variable (Y-
axis) is temperature.
• Phase transitions happen at the
specific temperature for most pure
substances.
• One important feature of cooling
curve is the solid horizontal line.
➢ At this particular point, Liquid
exist in an equilibrium state with
 2. Solve for m
𝑚 = ∆𝑇𝑓 /𝑘𝑓

m = 2.60 °C/ 6.94 ° C/m

= 0.375 m S8

3. Solve for mol S8

• Extrapolation is necessary because
as the solution freezes the solid that 𝑚 = 𝑚𝑜𝑙𝑠𝑜𝑙𝑢𝑡𝑒 /𝑘𝑠𝑜𝑙𝑣𝑒𝑛𝑡
is formed is essentially pure solvent. 1 𝑘𝑔
The remaining solution becomes 𝑚𝑜𝑙 𝑆8 = 0.375 𝑚 𝑆8 𝑥 15.10 𝐶10 𝐻8 ( )
1000 𝑔
more and more concentrated and its
freezing point becomes lower and 𝑚𝑜𝑙 𝑆8 = 5.66 𝑥 10−3 𝑚𝑜𝑙 𝑆8
lower.
• Supercooling (also known as
undercooling) 4. Solve for the molar mass 𝑆8
o the process of lowering the
temperature below its 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = 𝑚𝑎𝑠𝑠/ 𝑚𝑜𝑙
freezing point without it molar mass 𝑆8 = 1.50 𝑔 𝑆 / 5.66 𝑥 10−3 𝑚𝑜𝑙
becoming a solid.
o introduces an ambiguity in the molar mass 𝑆8 = 265 𝑔/𝑚𝑜𝑙
freezing point and should be
minimized using through
stirring. 5. Solve for the %error
𝑘𝑛𝑜𝑤𝑛 − 𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑
%𝑒𝑟𝑟𝑜𝑟 = | | 𝑥 100%
𝑘𝑛𝑜𝑤𝑛
Sample Calculations
1. Solve for ∆𝑇𝑓
256.52 𝑔/𝑚𝑜𝑙 − 265 𝑔/𝑚𝑜𝑙
%𝑒𝑟𝑟𝑜𝑟 = | | 𝑥 100%
∆𝑇𝑓 = 𝑘𝑓 𝑚 256.52
%𝑒𝑟𝑟𝑜𝑟 = 3.3%
• use the solution:
∆𝑇𝑓 = 𝑇𝑓 (𝑝𝑢𝑟𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡) − 𝑇𝑓 (𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛)

Given:
𝑇𝑓 𝑜𝑓 𝑝𝑢𝑟𝑒 𝑛𝑎𝑝𝑡ℎ𝑎𝑙𝑒𝑛𝑒 = 80.40 °𝐶

𝑇𝑓 𝑜𝑓 𝑝𝑢𝑟𝑒 𝑛𝑎𝑝𝑡ℎ𝑎𝑙𝑒𝑛𝑒 𝑤𝑖𝑡ℎ 𝑠𝑢𝑙𝑓𝑢𝑟 = 77.80 °𝐶

Solution:
∆𝑇𝑓 = 𝑇𝑓 (𝐶10 𝐻8 ) − 𝑇𝑓 (𝐶10 𝐻8 + 𝑆8 )

= 2.60 °𝐶
 Expt 10: Chemical Equilibrium
Le
Le Chatelier’s
Chatelier’s principle
reversible reactions
• A reversible reaction occurs when the
products of the reaction interact to
reform the initial substances.
𝑎𝐴(𝑔) + 𝑏(𝐵) ⇌ cC(g) + 𝑑𝐷(𝑔)
• Initial concentration of A and B will
decrease, and the concentration of C
and D will increase until the
concentration of all the substances
become constant.
• open system
➢ a reaction where the substances
can escape from the container
• close system
➢ a reaction where the substances
can't escape from the container.
• the forward and reverse reaction
continued to occur at equal opposed
balance rates (dynamic
equilibrium)
• no further relative concentration
changes occur
• At a given temperature, a chemical
system reaches a state of equilibrium
in which a particular ratio of reactant
and product concentration has a
constant value (K)
𝑎𝐴(𝑔) + 𝑏(𝐵) ⇌ cC(g) + 𝑑𝐷(𝑔)
[𝐶]𝑐 [𝐷]𝑑
𝐾=
[𝐴]𝑎 [𝐵]𝑏
➢ The lowercase letters represent
the coefficients of the substances
in the balance chemical equation.
➢ The uppercase letters
represents the reactants and the
products
principle
➢ Is the square brackets “[ ]” are
used then it means that the
substances are represented in a
molar concentration.
• There are several factors that can affect
the rate of the forward and reversible
reaction relative to the other can affect
the equilibrium position. (applicable only
in gaseous reactants)
a) temperature
b) concentration
c) pressure
• When some stress is applied to a system
originally in equilibrium, a system
reaction automatically will shift in such a
direction as to relieve the stress (for
example a change in concentration) and
reach a new state of equilibrium.
• Le Chatelier’s Principle
o states that if a dynamic
equilibrium is disturbed by
changing the conditions, the
position of equilibrium shifts to
counteract the change in order to
reestablish an equilibrium.
𝐴(𝑔) + (𝐵) ⇌ C(g)𝐷(𝑔)
increase shifts forward
in
conc
𝐴(𝑔) + (𝐵) ⇌ C(g)𝐷(𝑔)
shifts backward increase
in
conc
 acid-base indicators metal ion complex formation

• Many metallic ions form covalent

• Weak acids or weak bases that bonds with other ions or molecules
change color depending on the • Cobalt (II) chloride (CoCl2) was
acidity or basicity of its environment used in the experiment
• the acid base indicator used in the
experiment was methyl orange. Hexahydrous
Anhydrous
Pink to Purple
Blue CoCl2.6H2O

➢ HMO = acid form (non-ionized

form) of methyl orange.
➢ MO- = base form (ionized form) of
Tetrachloro
methyl orange cobaltate
• 14C, 14H, 3N, 1O (2-)
• Two differences can be observed •
(CoCl4-2)
In this experiment, we add HCl to
in the structure of acid and base CoCl2.6H2O
1. Acid form has a nitrogen • Addition of HCl, forms are blue
attached to the nitrogen chloride complex.
2. Formal charge on the ➢ Color: BLUE
nitrogen (acid=1, base= 0) ➢ Formula: CoCl42-
• Addition of H2O to the methyl orange (Tetrachlorocobaltate)
results in orange color. ➢ shift: right
• Addition of HCl increases the [H+], • Addition of H2O to previous solution,
shifting the equilibrium in reverse. forms a pink hydrate.
➢ Color: RED ➢ Color: PINK
➢ shift: LEFT ➢ Formula: Co(H2O)6+2
• addition of NaOH decreases the [H+], (Hexaaquacobalt (II) ion)
shifting the equilibrium forward ➢ shift: left
➢ Color: ORANGE
➢ shift: RIGHT
𝐻 + (𝑎𝑞) + 𝑂𝐻− → 𝐻2 𝑂 (𝑙)
effect of change of temperature • When the solution is heated, it turns
blue.
➢ Color: BLUE
• Heat will be treated as a reactant in ➢ Shift: RIGHT
an endothermic reaction, and as a ➢ Formula: CoCl42-
product in an exothermic reaction. (Cobalt chloride complex)

• When the solution is immersed in tap

water makes blue turned back to
pink.
➢ Color: PINK
➢ Shift: LEFT

equilibrium of slightly soluble solid

+ heat
exothermic
• For slightly soluble salts, a very small
𝐶𝑜(𝐻2𝑂)26 + 4 𝐶𝑙 − (𝑎𝑞) ⇌ CoC𝑙42− (𝑎𝑞) + 6𝐻2𝑂 amount will be dissolved in the
+ heat solvent (e.g. water) as associated
endothermic ions. There is an equilibrium between
the solid salt and the salt ions.
• Heating makes the solution turn
BLUE.
• In an endothermic reaction
➢ heat is treated as reactant
➢ 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
➢ Heat is added in the reactant
side.
➢ Meaning, heat is absorbed by
the system.
• In an exothermic reaction
➢ heat is treated as product
➢ 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
➢ Heat is added on the product 𝑍𝑛2+ (𝑎𝑞) + 2 𝑂𝐻 − (𝑎𝑞) ⇌ Zn(OH)2 (𝑠)
side
➢ Meaning, heat is released by • In the experiment, the effect of ion
the system in order to form zinc in magnesium ions was
the products. observed.
• From the previous solution, we have • Classified as double displacement
pink colored complex. CoCl2 + H2O reaction
• Sodium Nitrate is the system.
dissolving slightly soluble solid
➢ Adding more NaOH, it will
react to zinc ion to form ZN
• Adding H+ have to hydroxide solids (OH)42- complex
will decrease the OH-, favoring this (Tetrahydroxyzincate ion
dissolution of the salt. complex)
➢ The zinc ion will slowly
decrease
➢ Adding more Hydroxide
favors the dissolution
resulting to the dissolving of
the salt (clear solution)
➢ Shift: LEFT
➢ Result: ZN (OH)42- complex
(Tetrahydroxyzincate ion
complex)
• In the 3rd test tube (NH3)
➢ Addition NH3 turns the ZN2+
to Zn(NH3)4 2+(aq)
➢ same reaction with the
previous two.
• In each three test tubes, we add HCl, ➢ increases the solubility of the
NaOH, and NH3, respectively. zinc hydroxide
• In 1st test tube (HCl) ➢ Shift: LEFT
➢ Addition of H+ neutralizes OH- ➢ Result: Zn (NH3)4 2+(aq)
to water. complex (Tetraamminezinc
➢ neutralizes hydroxide to (II) ion complex)
water.
➢ in turn, the concentration will
decrease equilibrium of slightly soluble solid
➢ Shift: LEFT
➢ Favoring the DISSOLUTION • Zn2+ and Mg2+ are similar that both of
of the salt. Meaning, when them forms likely soluble hydroxides
adding more acid to zinc
hydroxide system, the salt will
start to dissolve resulting to a
clear solution.
• In 2nd test tube (NaOH)
➢ Addition of more OH- turns
the ZN2+ to ZN (OH)42-
complex
 ➢ white and cloudy precipitate.
➢ Addition of H+ neutralizes OH- to
water. In turn, decreases the
concentration of hydroxide
favoring the dissolution.
➢ Shift: Left
➢ The salt will dissolve when adding
acid to the system.

• Difference between Zn and Mg

➢ It does not form metal ion
complexes with OH- nor with
NH3 addition of more OH
minus or NH3 has an effect on
the solubility of the Mg (OH)2-
• When Ammonia is added:

Mg2+(aq) + NH3(aq) + 2H2O(l) ⇌

Mg(OH)2(s) + NH4+(aq)
• When Hydroxide ion is added

Mg2+(aq) + 2 OH- ⇌ Mg(OH)2(s)

• Addition of Hydroxide or Ammonia
will not favor the dissolution of the
salt. In turn, increasing the production
of solid and decreasing the solubility
• Shift: RIGHT
 Expt 11: Ph and Dissociation Constant
of
of boric
boric acid
acid and
and ammonia
ammonia

objective ionization of weak acids and bases

• Acid dissociation constant of

• The determine the dissociation
constants of a weak acid, boric acid, + −
𝐻𝐴(𝑎𝑞) + 𝐻2 𝑂(𝑙 ) ⇌ 𝐻3 𝑂 (𝑎𝑞) + 𝐴 (𝑎𝑞)
and a weak base, ammonia.
[𝐻3 𝑂+ ][𝐴− ]
𝐾𝑎 =
[𝐻𝐴]
➢ HA = concentration of acid at
equilibrium
Acids and bases
➢ A- = conjugate base at equilibrium

• Basic dissociation constant of

+ −
𝐵(𝑎𝑞) + 𝐻2 𝑂 (𝑙 ) ⇌ B𝐻 (𝑎𝑞) + 𝑂𝐻 (𝑎𝑞)
[𝐵𝐻][𝑂𝐻 − ]
𝐾𝑏 =
[𝐵]
• weak acids and weak bases are only ➢ B = concentration of base at
partially ionized in solution. equilibrium
• Strong acids and strong bases are ➢ OH- = conjugate acid at
completely ionized when dissolved in equilibrium
water.
• summary list of characteristics for
strong and weak acids and bases.

Characteristic Strong Weak

Acid and Acid and
Base Base
Molecules few Large
number
ions Large Small
number number
Conductivity Strong Weak
Bond strength Weak strong

• Common Strong acids and bases

➢ HCl, HNO3, H3SO4, HBr,
HClO4, HClO3 — Acids
➢ NaOH, KOH, Ba(OH)2,
Ca(OH)2 — Bases
 pH scale experiment

• A simple method to determine the • Serial Dilution

acid dissociation constant - a series of dilutions
• a measure of acidity/ basicity by
concentration of H3O+ ions, or [H3O+],
or [H+]
• Formula:
➢ pH= -log[H+]
➢ pOH= -log[OH-]

• First part
➢ prepare the different solutions
of different pH
➢ preparation of standard
solution from pH 3 - pH 11
➢ the solutions were prepared
• The stronger the acid the lower the by serial dilution
pH level ➢ as more solvent is added to
• Autoionization of water: the previous solvent, the
concentration of the solution
𝐾𝑤 = 1.0 𝑥 10−14 = [𝐻3 𝑂 + ] 𝑥 [𝑂𝐻 − ] will decrease.
• 2nd part
➢ Find the colors that are
• The stronger the acid, the higher the
characteristic of some
Ka.
indicators of solution of
• The weaker the acid, the lower the Ka. different pH.
o Different indicators exhibit
different colors at different
pH.
 calculations
For Boric Acid

• an example of triprotic acid

• the first dissociation constant, Ka1, of
boric acid is 1.0 x 10-10

H3BO3 + H2O ⇌ H2BO3- + H3O+

@ start 0.01 0 0
-x +x +x
@ equil 0.01 – x x x

Kb = x2
0.01 - x
• 3rd Part
with ph + 6, pH = -log [H3O+]
➢ compare the color of the boric [H3O+] = 10-pH = 10-6 = 1 x 10-6 = x
acid solution and ammonia
solution mixed with each
indicator (methyl orange, Ka1 = [H2BO3+][H3O+] / [H3BO3]
methyl red, bromthymol blue,
phenolphthalein, alizarin = (1 x 10-6)(1 x 10-6) / ( 0.01 – 1 x 10.-6)
yellow) = 1.0 x 10-10
➢ by color comparison, pH of
boric acid is 6 while For Ammonia
ammonia is 11. • the first dissociation constant, Ka1, of
Indicator Color of Color with boric acid is 2.0 x 10-5
used H3B3 (aq) NH3 (aq)
NH3 + H2O ⇌ NH4+ + OH-
Methyl Yellow Yellow @ start 0.05 0 0
orange orange -x +x +x
Methyl red Yellow Yellow @ equil 0.05 – x x x
Bromthymol Yellow Blue Kb = x2
blue 0.05 - x
H2pH Colorless Dark pink with pH = 11,
Alizarin Light yellow Light red
pKw = pH + pOH (is equal to 14)
yellow
pOH= pKw – pH = -log [OH-] = 14 – 11 = 3
[OH-] = 10 -pOH = 10-3 = 1 x 10-3 = x
Kb = [NH4+][OH-]/[NH3] = (1 x 10 -3)(1 x 10-3) /
(0.05 – 1 x 10-3)
= 2.0 x 10-5
*****end*****