Solution: DPP-2 [Vapour Pressure]

Chapter: Solution
”Consistency is the bridge between goals and accomplishment.”

TYPE–1 : Basic Concepts of Vapour Pressure

1. In liquid-gas equilibrium, the pressure of vapours above the liquid is constant at
(1) Constant temperature
(2) Low temperature
(3) High temperature
(4) None of these
Ans: (1) Constant temperature
Solution: Vapour pressure is an equilibrium property. At a given constant temperature, the rate of
evaporation equals the rate of condensation, and the vapour pressure remains constant. It depends
only on temperature, not on the amount of liquid or vapour present.
2. Vapour pressure is the pressure exerted by vapours
(1) In equilibrium with liquid
(2) In any condition
(3) In an open system
(4) In atmospheric conditions
Ans: (1) In equilibrium with liquid
Solution: Vapour pressure is defined as the pressure exerted by the vapour in thermodynamic
equilibrium with its condensed phase (liquid or solid) at a given temperature in a closed system.
3. The vapour pressure of water depends upon:
(A) Surface area of container
(B) Volume of container
(C) Temperature
(D) All
Ans: (C) Temperature
Solution: Vapour pressure is an intensive property that depends only on temperature and the
nature of the liquid. It does not depend on surface area, volume, or amount of liquid. As temperature
increases, more molecules have sufficient energy to escape, so vapour pressure increases.
4. During evaporation of liquid
(1) The temperature of liquid rises
(2) The temperature of liquid falls
(3) The temperature of liquid remains unaffected
(4) The liquid molecules become inert
Ans: (2) The temperature of liquid falls
Solution: Evaporation is a cooling process. During evaporation, the molecules with higher kinetic

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 energy escape from the liquid surface, leaving behind molecules with lower average kinetic energy.
Since temperature is proportional to average kinetic energy, the temperature of the remaining liquid
decreases.

TYPE–2 : Boiling Point & Vapour Pressure Relationship

1. The boiling points of C6H6, CH3OH, C6H5NH2, and C6H5NO2 are 80°C, 65°C, 184°C
and 212°C respectively. Which of the following will have highest vapour pressure at
room temperature?
(1) C6H6
(2) CH3OH
(3) C6H5NH2
(4) C6H5NO2
Ans: (2) CH3OH
Solution: Lower boiling point ⇒ Weaker intermolecular forces ⇒ Higher vapour pressure at room
temperature.
CH3OH has the lowest boiling point (65°C), so it has the highest vapour pressure at room tempera-
ture.
Order of VP: CH3OH > C6H6 > C6H5NH2 > C6H5NO2
2. The boiling points of C4H6, CH3OH, C4H5NH2, and C5H5NO2 are 80°C, 65°C, 184°C
and 212°C respectively. Which will show highest vapour pressure at room temperature:
(1) C4H6
(2) CH3OH
(3) C4H5NH2
(4) C5H5NO2
Ans: (1) C4H6
Solution: Note: In this question, we need to compare vapour pressures at room temperature (25°C).
All given boiling points are above room temperature. But C4H6 (butyne/butadiene) with BP = 80°C
is closest to room temperature among the options if we consider it’s actually a low BP compound.
Actually, C4H6 (1,3-butadiene) has BP ≈ -4°C, which is below room temperature, making it the
most volatile. The question seems to have an error in the given BP values, but based on the answer
key, C4H6 has the highest vapour pressure.
3. The temperature at which the vapour pressure of a liquid equals external pressure is
called
(1) Freezing point
(2) Boiling point
(3) Melting point
(4) Critical temperature
Ans: (2) Boiling point
Solution: By definition, boiling point is the temperature at which the vapour pressure of a liquid
equals the external (atmospheric) pressure. At this point, vapour bubbles can form throughout the
liquid, not just at the surface.
At 1 atm pressure, this is called the normal boiling point.
4. At higher altitude, the boiling point of water is lowered because

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 (1) Atmospheric pressure is low
(2) Temperature is low
(3) Atmospheric pressure increases
(4) Water solidifies to ice
Ans: (1) Atmospheric pressure is low
Solution: At higher altitudes, atmospheric pressure decreases. Since boiling occurs when vapour
pressure equals external pressure, water needs to reach a lower vapour pressure to boil. This happens
at a lower temperature.
For example: At Mt. Everest (≈ 0.34 atm), water boils at about 70°C.
5. At higher altitudes, water boils at temperature < 100°C because
(A) Temperature at higher altitudes is low
(B) Atmospheric pressure is low
(C) The proportion of heavy water increases
(D) Atmospheric pressure becomes more
Ans: (B) Atmospheric pressure is low
Solution: Same concept as above. Lower atmospheric pressure at higher altitudes means the vapour
pressure of water equals the external pressure at a temperature below 100°C.
6. Vapour pressure diagram of some liquids plotted against temperature are shown below

[Refer to question paper for graph]

Most volatile liquid

(1) A
(2) B
(3) C
(4) D
Ans: (1) A
Solution: In a P vs T graph, the liquid with the highest vapour pressure at any given temperature
is the most volatile.
From the graph, at any temperature, curve A is at the top (highest P value), meaning liquid A has
the highest vapour pressure ⇒ A is the most volatile.
Order of volatility: A > B > C > D
7. On the basis of intermolecular forces predict the correct order of decreasing boiling
points of the compounds:
(1) CH3OH > H2 > CH4
(2) CH3OH > CH4 > H2
(3) CH4 > CH3OH > H2
(4) H2 > CH4 > CH3OH
Ans: (2) CH3OH > CH4 > H2
Solution:
• CH3OH: Has hydrogen bonding (strongest IMF) ⇒ Highest BP (64.7°C)
• CH4: Only London dispersion forces, MW = 16 ⇒ BP = -161°C
• H2: Only London dispersion forces, MW = 2 (smallest) ⇒ Lowest BP (-253°C)
Stronger IMF ⇒ Higher boiling point

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TYPE–3 : Volatility & Intermolecular Forces
1. Among the following substances, the lowest vapour pressure is exerted by:
(A) Water
(B) Mercury
(C) Acetone
(D) Ethanol
Ans: (B) Mercury
Solution: Mercury is a metal with very strong metallic bonding. It has extremely low vapour
pressure at room temperature (≈ 0.002 mmHg at 25°C).
Order of VP: Acetone > Ethanol > Water > Mercury
Mercury’s VP is so low that it’s often considered negligible in many calculations.
2. Which of the following is correct? [NSEC-2017]
A liquid with
(A) low vapour pressure will have a low surface tension and high boiling point
(B) high vapour pressure will have high intermolecular forces and high boiling point
(C) low vapour pressure will have high surface tension and high boiling point
(D) low vapour pressure will have low surface tension and low boiling point
Ans: (C) low vapour pressure will have high surface tension and high boiling point
Solution: The relationship between these properties:
IMF Vapour Pressure Surface Tension Boiling Point
Strong Low High High
Weak High Low Low
Low VP ⇒ Strong IMF ⇒ High surface tension + High BP

TYPE–4 : Effect of Solute on Vapour Pressure

1. An aqueous solution is 1.00 molal in KI. Which change will cause the vapour pressure
of the solution to increase?
(1) Addition of water
(2) Addition of NaCl
(3) Addition of Na2SO4
(4) Addition of 1.00 molal KI
Ans: (1) Addition of water
0
Solution: According to Raoult’s Law: Psolution = xsolvent × Psolvent
Adding water (solvent) increases the mole fraction of solvent (xsolvent ), which increases the vapour
pressure of the solution.
Adding any solute (NaCl, Na2SO4, or more KI) would decrease xsolvent and thus decrease the vapour
pressure.

TYPE–5 : Conceptual & Application Based

1. A liquid is kept in a closed vessel. If a glass plate (negligible mass) with a small hole is
kept on top of the liquid surface, then the vapour pressure of the liquid in the vessel is:

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 (A) More than what would be if the glass plate were removed
(B) Same as what would be if the glass plate were removed
(C) Less than what would be if the glass plate were removed
(D) Cannot be predicted
Ans: (B) Same as what would be if the glass plate were removed
Solution: Vapour pressure is an equilibrium property that depends only on:
• Temperature
• Nature of the liquid
It does NOT depend on:
• Surface area of the liquid
• Volume of the container
• Presence of obstacles like glass plates
The glass plate with a hole will only slow down the rate of reaching equilibrium, but the final
equilibrium vapour pressure remains the same.
2. The vapour pressure of water at 20°C is 17.54 mmHg. What will be the vapour pressure
of the water in the apparatus shown after the piston is lowered, decreasing the volume of
the gas above the liquid to one half of its initial volume (assume temperature constant)?

[Refer to question paper for diagram]

(A) 8.77 mmHg

(B) 17.54 mmHg
(C) 35.08 mmHg
(D) Between 8.77 and 17.54 mmHg
Ans: (B) 17.54 mmHg
Solution: Key concept: Vapour pressure depends only on temperature, not on volume.
When the piston is lowered:
• Volume decreases to half
• Momentarily, the vapour would be compressed
• But since liquid water is present, some vapour will condense
• Equilibrium is re-established at the same temperature
• Final VP = 17.54 mmHg (unchanged)
Note: Boyle’s law (P1 V1 = P2 V2 ) does NOT apply here because the system is in equilibrium with
liquid water, which acts as a reservoir.

TYPE–6 : Numerical Problem

1. The vapor pressure of water at 80°C is 355 torr. A 100 mL vessel contained water-
saturated oxygen at 80°C, the total gas pressure being 760 torr. The contents of the
vessel were pumped into a 50.0 mL vessel at the same temperature. What were the
partial pressures of oxygen and of water vapor, and what was the total pressure in the
final equilibrated state? Neglect the volume of any water which might condense.
Ans: PO2 = 810 mm Hg, PH2O = 355 mm Hg, Ptotal = 1165 mm Hg
Solution:

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Step 1: Find initial PO2 in 100 mL vessel

PO2 = Ptotal − PH2O = 760 − 355 = 405 torr

Step 2: Apply Boyle’s law for O2 (non-condensable gas)

P1 V1 = P2 V2

405 × 100 = P2 × 50
405 × 100
PO 2 = = 810 torr
50
Step 3: Find PH2O in new vessel
Water vapour pressure depends only on temperature, not volume. Since T = 80°C (constant):

PH2O = 355 torr (unchanged)

Some water vapour will condense to maintain this equilibrium pressure.

Step 4: Calculate total pressure

Ptotal = PO2 + PH2O = 810 + 355 = 1165 torr