Physical and Analytical Chemistry - PYQ May 2023
Expert Examiner Solutions | Zero-Mark Deduction Format
Part A - Question 1 (Marks: 1)
Two components A and B exhibit positive deviation from ideality in a solution due to
  • (A) Weaker intermolecular forces between A-A and B-B compared to A-B
  • (B) Stronger intermolecular forces between A-B compared to A-A and B-B
  • (C) Stronger intermolecular forces between A-A compared to A-B and B-B
  • (D) Stronger intermolecular forces between A-A and B-B compared to A-B
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Correct Answer: (D) Stronger intermolecular forces between A-A and B-B compared to A-B
Detailed Reason:
A solution shows positive deviation from Raoult's Law when the cohesive forces between like molecules (A-A and B-B interactions) are stronger than the adhesive forces between unlike molecules (A-B interactions). Because the A-B attraction is weaker, molecules can escape more easily into the vapor phase, resulting in a higher vapor pressure than predicted by Raoult's Law.
Part A - Question 2 (Marks: 1)
Phenol and water are
  • (A) Immiscible
  • (B) Partially miscible
  • (C) Completely miscible
  • (D) Solids
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Correct Answer: (B) Partially miscible
Detailed Reason:
Phenol and water form a classic partially miscible liquid pair. At room temperature, they do not mix in all proportions and separate into two distinct liquid phases (a phenol-rich aqueous layer and a water-rich phenol layer). They only become completely miscible above their upper critical solution temperature (UCST) of approximately $66.8^\circ C$.
Part A - Question 3 (Marks: 1)
Which law specifically governs the relative lowering of vapour pressure in solutions?
  • (A) Raoult's law
  • (B) Henry's law
  • (C) Charles's law
  • (D) Boyle's law
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Correct Answer: (A) Raoult's law
Detailed Reason:
Raoult's Law states that the relative lowering of the vapor pressure of a dilute solution containing a non-volatile solute is equal to the mole fraction of the solute in the solution. Formula: $\frac{P^\circ - P}{P^\circ} = X_{solute}$.
Part A - Question 4 (Marks: 1)
On dissolving common salt in water
  • (A) The boiling point of the solution increases
  • (B) The boiling point of the solution decreases
  • (C) The vapour pressure is increased
  • (D) The freezing point is raised
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Correct Answer: (A) The boiling point of the solution increases
Detailed Reason:
Adding a non-volatile solute (like common salt, NaCl) to a solvent (water) lowers the vapor pressure of the solvent. As a result, a higher temperature is required for the vapor pressure to equal the atmospheric pressure, leading to an elevation in boiling point. It also causes a depression in freezing point.
Part A - Question 5 (Marks: 1)
Of the following equilibria, which one will shift to the left in response to a decrease in volume?
  • (A) $CO_2(g) + H_2O(l) \rightleftharpoons H_2CO_3(aq)$
  • (B) $H_2(g) + Cl_2(g) \rightleftharpoons 2HCl(g)$
  • (C) $N_2(g) + 3H_2(g) \rightleftharpoons 2NH_3(g)$
  • (D) $2SO_3(g) \rightleftharpoons 2SO_2(g) + O_2(g)$
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Correct Answer: (D) $2SO_3(g) \rightleftharpoons 2SO_2(g) + O_2(g)$
Detailed Reason:
According to Le Chatelier's principle, a decrease in volume (which causes an increase in pressure) shifts the equilibrium towards the side with the fewer number of moles of gas.
In reaction (D), there are 2 moles of gas on the left and 3 moles of gas on the right. Therefore, an increase in pressure will shift the equilibrium to the left (towards 2 moles).
Part A - Question 6 (Marks: 1)
Which of the following is a criterion for chemical equilibrium?
  • (A) Equality of concentration
  • (B) Equality of temperature
  • (C) Equality of pressure
  • (D) Equality of chemical potential
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Correct Answer: (D) Equality of chemical potential
Detailed Reason:
In thermodynamics, a multi-component system is in chemical equilibrium when the chemical potential ($\mu$) of each component is equal across all phases. This implies that there is no net driving force for matter to move from one phase to another or for a reaction to proceed in a net direction ($\Delta G = 0$).
Part A - Question 7 (Marks: 1)
Application of pressure to ice and water in equilibrium results in
  • (A) Decrease the melting temperature of ice
  • (B) Increase the temperature of ice
  • (C) Decrease in the boiling point of water
  • (D) Increase in the boiling point of water
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Correct Answer: (A) Decrease the melting temperature of ice
Detailed Reason:
Water is anomalous because its solid phase (ice) is less dense than its liquid phase. According to Le Chatelier's principle, applying pressure to an ice-water equilibrium will shift the system towards the denser phase (water) to relieve the pressure. Consequently, ice melts at a lower temperature under higher pressure, meaning the melting point decreases.
Part A - Question 8 (Marks: 1)
Which of the following is correct when the number of moles of products is equal to the number of moles of reactants?
  • (A) $K_p = 0$
  • (B) $K_p = K_c$
  • (C) $K_p < 0$
  • (D) $K_p = 1$
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Correct Answer: (B) $K_p = K_c$
Detailed Reason:
The relationship between $K_p$ and $K_c$ is given by $K_p = K_c(RT)^{\Delta n}$, where $\Delta n$ is the change in the number of moles of gas (moles of gaseous products - moles of gaseous reactants). When the number of moles is equal, $\Delta n = 0$. Since $(RT)^0 = 1$, the equation simplifies to $K_p = K_c$.
Part A - Question 9 (Marks: 1)
On heating a 10N aqueous solution to NaOH, the solubility of NaOH in water
  • (A) Increases
  • (B) Decreases
  • (C) Is unaltered
  • (D) Increases, then decreases
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Correct Answer: (A) Increases
Detailed Reason:
While the initial dissolution of NaOH in water is highly exothermic, the overall solubility curve of NaOH in water shows that its solubility increases with temperature. At higher temperatures, the kinetic energy of the solvent molecules increases, allowing them to break apart the solute crystal lattice more effectively.
Part A - Question 10 (Marks: 1)
The number of components in an aqueous sucrose solution is
  • (A) 1
  • (B) 2
  • (C) 3
  • (D) 4
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Correct Answer: (B) 2
Detailed Reason:
The number of components ($C$) in a system is the minimum number of independent chemical species required to define the composition of all phases in the system. An aqueous sucrose solution consists of water (solvent) and sucrose (solute), which do not react to form a new species. Thus, $C = 2$.
Part A - Question 11 (Marks: 1)
The number of degrees of freedom of a 3 component system at standard temperature and pressure is
  • (A) $1 - P$
  • (B) $2 - P$
  • (C) $3 - P$
  • (D) $4 - P$
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Correct Answer: (C) $3 - P$
Detailed Reason:
According to the Gibbs Phase Rule, $F = C - P + 2$.
For a 3-component system ($C=3$), $F = 3 - P + 2 = 5 - P$.
However, the question specifies that the system is at standard temperature and pressure. Since both Temperature and Pressure are fixed (held constant), they subtract 2 degrees of freedom from the system.
The condensed phase rule becomes $F = 5 - P - 2 = 3 - P$.
Part A - Question 12 (Marks: 1)
The corners of a triangle in a ternary plot represent the
  • (A) Binary mixtures
  • (B) Pure components
  • (C) Ternary mixtures
  • (D) Eutectic points
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Correct Answer: (B) Pure components
Detailed Reason:
In a ternary phase diagram (an equilateral triangle plot used for 3-component systems), each of the three apices (corners) corresponds to 100% composition of one of the three components. Thus, the corners represent the pure components.
Part A - Question 13 (Marks: 1)
Which of these equations gives the energy associated with a photon?
  • (A) $E = h/\lambda$
  • (B) $E = h\nu$
  • (C) $E = hc$
  • (D) $E = hc^2$
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Correct Answer: (B) $E = h\nu$
Detailed Reason:
According to the Planck-Einstein relation, the energy ($E$) of a single photon is directly proportional to its frequency ($\nu$). The equation is $E = h\nu$, where $h$ is Planck's constant. It can also be expressed as $E = hc/\lambda$.
Part A - Question 14 (Marks: 1)
If ferric chloride solution is added to a colloidal sol of ferric hydroxide, then the charge on the particles is
  • (A) Positive
  • (B) Negative
  • (C) Neutral
  • (D) Absent
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Correct Answer: (A) Positive
Detailed Reason:
When $FeCl_3$ is added to a precipitate of $Fe(OH)_3$, peptization occurs. The $Fe(OH)_3$ particles preferentially adsorb the common ion, which is $Fe^{3+}$ from the $FeCl_3$ solution, onto their surface. The adsorption of these cations imparts a positive charge to the colloidal particles.
Part A - Question 15 (Marks: 1)
The range of quantum yield for the photochemical reaction $H_2 + Cl_2 \rightarrow 2HCl$ is
  • (A) 10 to 100
  • (B) 0.001 to 0.1
  • (C) 0.1 to 1
  • (D) $10^4$ to $10^6$
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Correct Answer: (D) $10^4$ to $10^6$
Detailed Reason:
The photochemical reaction of hydrogen and chlorine is a classic example of a secondary chain reaction. A single photon cleaves a $Cl_2$ molecule into two highly reactive Cl free radicals. These radicals initiate a propagation chain that can produce up to a million molecules of HCl before termination occurs. Thus, the quantum yield ($\Phi$) is extraordinarily high, in the range of $10^4$ to $10^6$.
Part A - Question 16 (Marks: 1)
A sol is a stable suspension of
  • (A) Gas in liquid
  • (B) Solid in liquid
  • (C) Liquid in solid
  • (D) Liquid in gas
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Correct Answer: (B) Solid in liquid
Detailed Reason:
In colloid chemistry, a sol is defined as a colloidal suspension composed of very small solid particles dispersed within a continuous liquid medium (e.g., gold sol, paint, blood).
Part A - Question 17 (Marks: 1)
_____ is the uncertainity in any measurement.
  • (A) Precision
  • (B) Accuracy
  • (C) Error
  • (D) Calibration
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Correct Answer: (C) Error
Detailed Reason:
In analytical chemistry, Error refers to the difference between the measured value and the true or accepted value. It encapsulates the inherent uncertainty present in any physical measurement due to limitations in the instrument or the observer.
Part A - Question 18 (Marks: 1)
The non ideal chemical or physical behavior of the reagents and reactions on which an analysis is based often introduces _____ errors.
  • (A) Instrumental
  • (B) Method
  • (C) Personal
  • (D) Gross
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Correct Answer: (B) Method
Detailed Reason:
Method errors are systematic errors that are inherent to the analytical method itself. They arise from non-ideal behaviors such as incomplete reactions, co-precipitation, side reactions, or instability of reagents, which cannot be fixed merely by recalibrating the instrument.
Part A - Question 19 (Marks: 1)
Which of these does NOT belong to the monochromator unit?
  • (A) Collimating lens
  • (B) Prism
  • (C) Focusing lens
  • (D) Deuterium lamp
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Correct Answer: (D) Deuterium lamp
Detailed Reason:
A monochromator separates polychromatic light into distinct wavelengths and consists of an entrance slit, a collimator, a dispersing element (like a prism or grating), and a focusing lens. The Deuterium lamp is an external UV light source that feeds into the monochromator, not a component of the monochromator itself.
Part A - Question 20 (Marks: 1)
The _____ contains all the components of the original sample except the analyte.
  • (A) Standard
  • (B) Blank
  • (C) Reagent
  • (D) Emulsion
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Correct Answer: (B) Blank
Detailed Reason:
In spectrophotometry and analytical chemistry, a Blank solution is prepared to contain all the reagents and solvents present in the actual sample, omitting only the specific analyte being measured. It is used to zero the instrument and cancel out background absorbance caused by the matrix.