Roll No. Q.P.

Code 01
Candidates must write the Q.P. Code
on the title page of the answer-book.

SAMPLE QUESTION PAPER-1

CHEMISTRY

Time allowed: 3 hours Maximum Marks: 70

NOTE:
(i) Q.P. Code given on the right hand side of the question paper should be written on the title page of the answer-book by the
candidate.
(ii) Please check that this question paper contains 33 questions.
(iii) Please write down the Serial Number of the question in the answer-book before attempting it.
(iv) 15 minute time has been allotted to read this question paper. The students will read the question paper only and will not
write any answer on the answer-book during this period.

GENERAL INSTRUCTIONS:
Read the following instructions carefully and strictly follow them:
(i) There are 33 questions in this question paper with internal choice.

(ii) Section - A consists of 16 multiple - choice questions carrying 1 mark each.

(iii) Section - B consists of 5 very short answer questions carrying 2 marks each.

(iv) Section - C consists of 7 short answer questions carrying 3 marks each.

(v) Section - D consists of 2 case - based questions carrying 4 marks each.

(vi) Section - E consists of 3 long answer questions carrying 5 marks each.

(vii) All questions are compulsory.

(viii) Use of calculators is not allowed.

 SECTION - A
The following questions are multiple-choice questions with one correct answer. Each question carries 1 mark.
There is no internal choice in this section.
1. Which one is not equal to zero for an ideal solution? 1
(a) ∆Smix (b) ∆Vmix (c) ∆P = Pobserved – PRaoult
(d) ∆Hmix
2. Isotonic solutions have 1
(a) Same melting point (b) Same volume (c) Same boiling point (d) Same osmotic pressure
3. The unit of rate constant obeying the rate expression r = k[A]1[B]2/3 is 1
(a) mole–2/3 lit2/3 time–1 (b) mole2/3 lit–2/3 time–1 (c) mole–2/3 lit–2/3 time–1 (d) mole2/3 lit2/3 time–1
4. Which among the following is the correct order of no. of unpaired electron? 1
2+ 2+ 3+ 3+ 3+ 2+ 3+ 2+
(a) Cu > Ni > Cr > Fe (b) Cr > Cu > Fe > Ni
3+ 3+ 2+ 2+
(c) Fe > Cr > Ni > Cu (d) Cr3+ > Fe3+ > Ni2+ > Cu2+
5. Potassium dichromate is 1
(a) Strong oxidising agent (b) Strong reducing agent (c) Both (a) and (b) (d) None of these
6. In terms of field strength which is correct arrangement of ligands:1
(a) Cl– < F– < NCS– < NH3 < CN– (b) NH3 < CN– < NCS– < Cl– < F–
–
(c) Cl– < NH3 < NCS– < CN– < F (d) NH3 < F– < Cl– < NCS– < CN–
7. The magnetic moment value of coordination compound Cr(CO)6 is: 1
(a) 4.90 BM (b) 2.84 BM (c) 1.73 BM (d) 0 BM
8. When alkyl halide reacts with moist Ag2O gives 1
(a) Alcohol (b) Ether (c) Alkane (d) Alkene
9. ( CH3 )3 COCH3 
+ HI
→ ( CH3 )3 CI + CH3OH  1
Above reaction follows which mechanism?
(a) SN1 (b) SN2 (c) E1 (d) Both (b) and (c)
10. Propionic acid with Br2/P yields a dibromo product. Its structure would be 1

(a) (b) (c) (d)

11. Which among the given possess highest boiling point? 1

(a) CH3CH2Cl (b) CH3CHO (c) CH2CH2OH (d) CH3COOH
12. A mixture of amylose and amylopectin is called: 1
(a) Lactose (b) Starch (c) Cellulose (d) Sucrose

For Questions number 13 to 16, two statements are given - one labelled as Assertion (A) and the other labelled as
Reason (R). Select the correct answer to these questions from the codes (a), (b), (c) and (d) as given below.
(a) 
Both Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of Assertion (A).
(b) 
Both Assertion (A) and Reason (R) are true, but Reason (R) is not the correct explanation of Assertion (A).
(c) Assertion (A) is true, but Reason (R) is false.
(d) Assertion (A) is false, but Reason (R) is true.
13. Assertion (A): Conductivity of all electrolytes decreases on dilution.
Reason (R): On dilution number of ions per unit volume decreases. 1

64 CHEMISTRY – XII P
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 14. Assertion (A): Order and molecularity are same.
Reason (R): Order is determined experimentally and molecularity is the sum of the stoichiometric coefficient of rate determining
elementary step. 1
15. Assertion (A): The highest oxidation state of osmium is +8.
Reason (R): Osmium is a 5d-block element. 1
16. Assertion (A): Compounds containing —CHO group are easily oxidised to corresponding carboxylic acids.
Reason (R): Carboxylic acids can be reduced to alcohols by treatment with LiAlH4. 1

SECTION - B
This section contains 5 questions with internal choice in one question. The following questions are very short answer type
and carry 2 marks each.
17. Calculate the freezing point of a solution containing 60 g of glucose (Molar mass = 180 g mol–1) in 250 g of water.
(Kf of water = 1.86 K kg mol–1) 2
18. (a) How would you obtained acetophenone from phenol? 1+1=2
(b) Write a short note on Kolbe’s reaction.
19. How do you convert the following? 1+1=2
(a) Ethanal to Propanone
(b) Toluene to Benzoic acid
OR
(a) What product is obtained when butanoic acid reacts with Br2/P? 1+1=2
(b) R—COOH  
LiAlH 4
H3O

20. Draw the structure of amylopectin, and how are its glucose units linked together? 2
21. (a) Given that the standard electrode potentials (E°) of metals are: 1+1=2
+ + +2
K /K = –2.93 V, Ag /Ag = 0.80 V, Cu /Cu = 0.34 V,
Mg2+/Mg = –2.37 V,Cr3+/Cr = –0.74 V, Fe2+/Fe = –0.44 V
Arrange these metals in increasing order of their reducing power.
(b) What are the differences between primary and secondary batteries?

SECTION - C
This section contains 7 questions with internal choice in one question. The following questions are short answer types
and carry 3 marks each.
22. (a) The cell in which the following reaction occurs:  3
3+ – 2+
2Fe (aq) + 2I (aq) → 2Fe (aq) + I2(s) has E°cell = 0.236 V at 298 K. Calculate the standard Gibbs energy of the cell
reaction. (Given : 1F = 96,500 C mol –1)
(b) How many electrons flow through a metallic wire if a current of 0.5 A is passed for 2 hours? (Given : 1F = 96,000 C mol –1)
23. (a) Define conductivity and molar conductivity for the solution of an electrolyte. Discuss their variation with change in
temperature. 2+1=3
(b) Calculate the time to deposit 1.27 g of copper at cathode when a current of 2A was passed through the solution of CuSO4.
(Molar mass of Cu = 63.5 g mol–1, 1 F = 96500 C mol–1)
24. (a) Describe the reaction of phenol with a mixture of potassium dichromate (K2Cr2O7) and sulfuric acid (H2SO4). Write the
chemical equation and explain the observations. 1½ + 1½ = 3
(b) What is the product when phenols undergo electrophilic aromatic substitution with bromine (Br2)?

Sample Question Paper-1 65

25. Write the major product(s) in the following: (Any three) 3×1=3
(i) DIBAL–H
(a) CH3–CH=CH–CN
(ii) H3O+
CrO3
(b) CH3–CH2–OH
D
(c) HCHO + Conc. KOH
NaOH
(d) CH 3 − CH 2 − CHO  →
26. (a) Discuss the synthetic utility of the Hoffmann bromamide reaction in the preparation of primary amines. Provide an
example of the reaction with the corresponding product.  1½ + 1½ = 3
(b) Write the mechanism of acylation of amine.
27. (a) Which aromatic amine is used in the synthesis of azo dyes? Give its chemical reactions. 1½ + 1½ = 3
(b) How will you distinguish between a primary and secondary amine?
28. Explain Henry’s law and how it relates to the solubility of gases in liquids. Provide an example of a gas-liquid solution? 3

SECTION - D
The following questions are case-based questions. Each question has an internal choice and carries 4 marks each.
Read the passage carefully and answer the questions that follow.
29. The f-block elements are characterized by the filling of (n-2)f orbitals with differentiating electrons. These elements consist
of two series, one with 4f-orbitals filling and the other with 5f-orbitals filling. The series involving 4f-orbitals is referred
to as lanthanides. Lanthanides exhibit various oxidation states, with +3 being the most common. Stability of f0, f7, and f14
configurations determines the observed oxidation states. Additionally, there is a regular reduction in the size of lanthanide
ions as atomic number increases, which is known as lanthanides contraction.
(a) Which lanthanide element shows the maximum number of oxidation states, and what are the values of these oxidation
states? 1
OR
(a) Explain why lanthanides commonly found in +3 oxidation state and provide an example of a lanthanide ion in this
oxidation state. 1
(b) What term is used to describe the gradual reduction in the size of lanthanide ions as atomic number increases? 1
(c) (i) The team of researchers is studying the properties of europium, a lanthanide element. They observe that europium
can form compounds with +2 and +3 oxidation states. Describe the electronic configuration change when europium
undergoes these oxidation states. 2×1=2
(ii) Describe the phenomenon of “Lanthanides Contraction” and its implications on the properties of lanthanide ions.
30. After watching a programme on TV about the presence of carcinogens (cancer causing agents) Potassium bromate and Potassium
iodate in bread and other bakery products, Rupali a Class XII student decided to make others aware about the adverse effects
of these carcinogens in foods. She consulted the school principal and requested him to instruct the canteen contractor to stop
selling sandwiches, pizzas, burgers and other bakery products to the students. The principal took an immediate action and
instructed the canteen contractor to replace the bakery products with some protein and vitamin rich food like fruits, salads,
sprouts, etc. The decision was welcomed by the parents and the students.
After reading the above passage, answer the following questions: 4×1=4
(a) What are the values (at least two) displayed by Rupali?
(b) Which polysaccharide component of carbohydrates is commonly present in bread?
(c) Write the two types of secondary structures of proteins.
(d) What are water soluble vitamins? Gives its two examples.

66 CHEMISTRY – XII P
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 SECTION - E
The following questions are long answer types and carry 5 marks each. All questions have an internal choice.
31. The decomposition of C6H5NH2 (aniline) is studied at a constant volume, and the concentration of C6H5NH2 at different times
is recorded: 2+1+2=5
Time (s) [C6H5NH2] (mol/L)
0 0.3
100 0.24
200 0.19
300 0.152
(a) Calculate the rate constant (k) for the first-order decomposition of C6H5NH2 ( Use ln 0.5067 = – 0.679)
(b) Determine the half-life of the reaction.
(c) Find the concentration of C6H5NH2 after 400 seconds. (Use e–0.92 = 0.398)
OR
(a) Why does a first-order reaction have a constant half-life? 1+1+3=5
2
(b) For a reaction A + B → P, the rate is given by Rate = k[A] [B]
What is the overall order of reaction if B is present in large excess?
(c) What is the activation energy for a reaction if its rate constant increases by a factor of 10 when the temperature is increased
from 25°C to 50°C?
32. (a) Describe the concept of Crystal Field Stabilization Energy (CFSE) in octahedral complexes and provide diagrams to
illustrate the explanation. 4+1=5
(b) What is the coordination isomerism explain with the help of example.
OR
(a) Describe the concept of Crystal Field Stabilization Energy (CFSE) in tetrahedral complexes, and provide diagrams to
illustrate the explanation. 4+1=5
(b) What is the difference between an ambidentate ligand and a chelating ligand ?
33. Attempt any five of the following: 5×1=5
Complete the following reactions.
(a) Bromoethane to butane
(b) Bromoethane to 1– butyne
(c) Bromoethane to ethoxyethane
(d) 1–chloropropane to 1– nitropropane
(e) Propanol to 1 – chloropropane
(f) Bromobutane to butene
(g) Bromoethane to Iodoethane

Sample Question Paper-1 67

 SAMPLE QUESTION PAPER-1
(Explanations)
1. (a) ΔSmix > 0 15. (b) Osmium is 5d-block elements having highest O.S.
As entropy increases after mixing. (1 M) i.e. +8. (1 M)
2. (d) Same osmotic pressure solutions are known as 16. (b) Aldehydes are oxidised to carboxylic acid by mild
isotonic solutions. (1 M) oxidising agents and reduced to alcohol by reducing
3. (a) Mole–2/3 lit2/3 time–1 (1 M) agents. (1 M)
–1
4. (c) Fe+3 = 3d54s0 = = 5 unpaired electrons 17. WB = 250 g, WA = 60 g, MA = 180 g mol

Kf = 1.86 K kg mol–1
Cr3+ = 3d34s0 = = 3 unpaired electrons
WA  1000
2+ 8
Ni = 3d 4s = 0
= 2 unpaired electrons DTf = Kfm  K f 
 (1 M)
M A  WB
Cu2+ = 3d94s0 = unpaired electron 60  1000 1.86  600 1116
 3d
5
4s
1
(1 M)  1.86     2  48 K
180  250 18  25 450
5. (a) Potassium dichromate is a strong oxidising agent.
DTf = Tsolvent – Tsolution

 (1 M)
– – –
6. (a) Cl < F < NCS < NH3 < CN . –
(1 M) Tsolution = Tsolvent – DTf
7. (d) Cr(CO)6 ⇒ x + 0 = 0 = 273 . 15 K – 2 . 48 K
Cr =
= = 270 . 67 K or – 2 . 48°c (1 M)
5 1
3d 4s Topper’s Explanation (CBSE 2018)
CO is a strong ligand so pairing will takes place
Cr =
no unpaired electron is present therefore, μ = 0(1 M)
8. (a) Alcohol (1 M)
9. (a) Given reaction follows SN1 mechanism. (1 M)
10. (c) This is Hell - Volhard-Zelinsky reaction.

 (1 M)

11. (d) Among the given, CH3COOH possess highest boiling

point due to presence of more number of H-bonds.
 (1 M)
12. (b) A mixture of amylose and amylopectin is called
starch. (1 M)
13. (a) Conductivity depends on the number of ions per
unit volume. Therefore, conductivity of electrolysis OH COCH3
18. (a)
decrease on dilution due to decrease in number of
ions per unit volume. (1 M)
Zn dust, D CH3COCl
14. (d) Order and Molecularity are not same order is –ZnO Anhyd, AlCl3
determined by experimentally and Molecularity is
the sum of the Stoichiometric Coefficient of rate Phenol Acetophenone
determining step. (1 M)  (1 M)
 OR
(a) The reaction of butanoic acid in the presence of Br2/P
Mistakes 101 : What not to do! (Bromine and Phosphorus) leads to the formation of
2,2-dibromobutanoic acid.
Students mistake the reagent used for the reaction . Not
mentioning the need for a catalyst (e.g., anhydrous AlCl3) CH3CH2CH2COOH
Br2 /P
CH3CH2C(Br)2COOH
in the reaction. Butanoic acid
–2HBr
2,2-dibromo-
OH ONa OH  butanoic acid
COOH This reaction is known as Hell-Volhard Zelinsky
(b) reaction. (1 M)
(i) CO2
NaOH
(ii) H+

Phenol Ortho-hydroxybenzoic
Sodium
phenoxide acid (Salicylic acid)
Mistakes 101 : What not to do!

(1 M) Student incorrectly describing the bond formation

19. (a) Ethanal to Propanone between the propanoic acid molecule and the phosphorus
OMgBr atom in PBr3.

CH3CHO + CH3MgBr CH3 CH CH3 (b) R  COOH LiAlH

 4
 RCH 2 OH  (1 M)
H O
Ethanal
3

Hydrolysis 20. Amylopectin is a type of starch. Its structure is made up

CH3 CH OH
H2O/H+ of glucose units linked together through α-1, 4-glycosidic
CH3 bonds in linear chains while branching occurs by C1-C6
 Propan-2-ol glycosidic linkage. (½ M)
O CH2OH
KMnO4 H OH
CH3 C CH3
 Propanone OHH H
(1 M) O a-link
(b) Toluene to Benzoic acid H OH
CH3 COOK O
Branch at C6
KMnO4, KOH CH2 CH2OH
Heat H OH H OH
Toluene OHH H OHH H
COOH O O
O
H OH H OH
H3O+  (1 ½ M)

 Benzoic acid Mistakes 101 : What not to do!

(1 M)
Topper’s Explanation (CBSE 2018) Student confusing the linkage between glucose units in
amylopectin, such as assuming only α-1, 4-glycosidic
bonds or neglecting the presence of branching α-1,
6-glycosidic bonds.

21. (a) More the negative value of standard potential, ,more will
be the reducing power. According to the given values of
standard reduction potentials, the correct order is:
Ag+/Ag < Cu2+/Cu < Fe2+/Fe < Cr3+/Cr < Mg2+/Mg
< K+/K(1 M)

132 CHEMISTRY – XII P

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 (b) Primary batteries Secondary batteries
In these types of batteries,
These types of batteries Mistakes 101 : What not to do!
the reaction takes place can be recharged again
only once and after use by passing current Student Confusing the relationship of conductivity and
over a period of time,thethrough them in opposite molar conductivity with temperature.
battery becomes dead and directions so that these
cannot be reused again. can be used again. (b) CuSO4 → Cu+2 + SO42–
Examples: Dry cell, Examples: Lead storage Cu2+ + 2e– → Cu
mercury cell battery, nickel cadmium 63.5 gram of copper is deposited = 2 × 96500 C
cell 2  96500
(1 M) 1.27 gram of Cu is deposited   1.27
63.5
22. (a) DrG° = –nFE°cell 2  96500  1.27
 (n = 2 \ change in oxidation state by 2) t = 1930 seconds (1 M)
63.5  2
= –2 × 96500 × 0.236 = –45.548 kJ/mol (1½ M)
24. (a) Phenol undergoes oxidation with a mixture of
(b) It = 0.5 × 2 × 60 × 60C = 3600C potassium dichromate (K 2Cr 2O 7) and sulphuric
Charge; Q = It = ne acid (H2SO4) to form benzoquinone. The chemical
3600 = n × 1.60 × 10–19 equation for this reaction is:
3600 OH O
n   2.25  1022 electrons (1½ M)
19
1.60  10
Topper’s Explanation (CBSE 2017) K2Cr2O7

conc H2SO4 (1½ M)
[O]

O
phenol 1, 4-benzoquinone
(b) The product obtained is 2, 4, 6-tribromophenol.
Bromine substitutes the hydrogen atoms in the phenol
ring due to the presence of the electron-rich benzene
ring in phenols.
OH OH
Br Br
+ Br2 /water

Phenol Br
2,4,6-tribromophenol

23. (a) Conductivity: Conductivity of a solution is defined (1½ M)
as the conductance of a solution of 1 cm length and 25. (a) CH3 – CH = CH – CN
having 1 sq. cm as the area of cross-section. It is (i) DIBAL–H
represented by k. Its unit is S cm–1  CH3–CH=CH–CHO  (1 M)
(ii) H3O+
Molar conductivity : Molar conductivity of a
CrO3
solution at a dilution V is the conductance of all (b) CH3–CH2–OH CH3–CHO (1 M)
the ions produced from one mole of the electrolyte D –
dissolved in V cm3 of the solution when the electrodes (c) HCHO + conc. KOH CH3OH + HCOO K+
are 1 cm apart and the area of the electrodes is so large  (1 M)
that the whole of the solution is contained between (d) CH 3 − CH 2 − CHO 
NaOH
→
them. It is represented by lm. Its unit is S cm2 mol–1

(1 M) CH 3 − CH 2 − CH − CH 2 − CH 2 − CHO  (1 M)
|
As temperature rises conductivity and molar OH
conductivity both increase. (1 M)

Sample Question Paper-1 133

 26. (a) The Hoffmann bromamide reaction is a useful method leads to a decrease in solubility. This principle is vital for
for the preparation of primary amines with one carbon understanding gas-liquid interactions and plays a crucial
atom less than the original amide. It involves the role in various natural and industrial processes.(1 M)
reaction of a primary amide with excess bromine Example: A classic example of Henry’s Law is the
(Br2) and sodium hydroxide (NaOH). (½ M) solubility of oxygen (O2) in water. When the pressure
O of oxygen above water increases (as in contact with air
or during aeration), more oxygen molecules dissolve in
CH3 C NH2 + Br2 + 4KOH(aq) the water. This is why oxygen is transported from the air
D
CH3 NH2 + 2KBr + K2CO3 + 2H2O into aquatic environments enabling aquatic organisms to
 Methylamine respire.(1 M)
(1 M)
O H O 29. (a) Cerium (Ce) exhibits the maximum number of
oxidation states among lanthanides, with values of
(b) R N H + CH3 C Cl → R N C CH3 + 3 and + 4.(1 M)
O OR
H H
–H ­+ (a) In +3 oxidation state lanthanides lose three electrons
→ R NH C CH3 + HCl from their outermost 6s and 5d orbitals. This results
(1½ M) in a stable electronic configuration. So, lanthanides
27. (a) Aniline (C6H5-NH2) is the aromatic amine used in commonly found in +3 oxidation state.(1 M)
the synthesis of azo dyes.(½ M) (b) The term used to describe the gradual reduction in the
+ –
NH2 N2Cl size of lanthanide ions as atomic number increases is
“lanthanide contraction.”(1 M)
(c) (i) Europium has the electronic configuration [Xe]
NaNO2 + 2HCl
+ NaCl + 2H2O 4f7 6s2 in its neutral state. When europium forms
273 – 278 K
compounds with a +2 oxidation state, it loses
Aniline Benzenediazonium two outermost s-electrons and becomes [Xe]
chloride 4f7. In the +3 oxidation state, europium loses
(1 M) three outermost s-electrons, resulting in the
(b) The carbylamine test can be used to distinguish configuration [Xe] 4f 6. The loss of electrons
between a primary and secondary amine. from the outermost s-orbital leads to the different
When heated with chloroform and alcoholic oxidation states of europium.(1 M)
potassium hydroxide, primary amines produce a foul-
smelling isocyanide (carbylamine) while secondary
amines do not.(½ M) Nailing the Right Answer
D +
R NH2 + CHCl3 + 3KOH → R N ≡≡C When europium undergoes a change in oxidation state,
 + KCl + 3H2O there are electron configuration changes, which involve
(1 M) the loss of electrons from the outermost 6s2 and 4f7
orbitals. In the +2 oxidation state, europium loses two
electrons from the 6s2 orbital, while in the +3 oxidation
Nailing the Right Answer
state, it loses three electrons, two from the 6s2 orbital and
The Carbylamine reaction can be used to distinguish one from the 4f7 orbital.
between primary, secondary, and tertiary amines based
on the presence or absence of a foul-smelling isocyanide (ii) Lanthanides contraction is the regular decrease
or pungent odour upon reaction with chloroform and in the size of lanthanide ions with an increase
alcoholic potassium hydroxide. in atomic number. It affects various properties,
including atomic and ionic radii, ionization
28. Henry’s Law: Henry’s Law states that the solubility of enthalpy, and hydration enthalpy, leading
a gas in a liquid is directly proportional to the partial to differences in chemical reactivity and
pressure of the gas present above the surface of liquid at coordination behavior.(1 M)
a constant temperature.(1 M) 30. (a) Rupali cares about the harmful effects of cancer-
Relation to Gas Solubility: According to Henry’s Law, as the causing substances in food and wants people to be
partial pressure of a gas increases, its solubility in the liquid aware of them. (1 M)
also increases. Conversely, a decrease in the gas pressure (b) Starch is commonly present in bread. (1 M)

134 CHEMISTRY – XII P

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 (c) The different types of proteins called α-helix and [C6H5NH2] ≈ 0.3 × 0.398 ≈ 0.1194mol/L
β-pleated sheets. (1 M) The concentration of C6H5NH2 after 400 seconds is
(d) Vitamin-B and Vitamin-C both are water soluble approximately 0.1194 mol/L.(1 M)
vitamins. Water soluble vitamins are soluble in water OR
that must be supplied regularly through diet as they
(a) For a first order reaction,
get readily excreted from urine. (1 M)
Topper’s Explanation (CBSE 2017) t1/2= 0.693 /k (1 M)
Half life of first order reaction is independent of
initial concentration of reactants and hence, remains
constant over time.(1 M)
(b) k = [A]2B
If B is present in large excess, it can be neglected
with respect to A due to which the overall order of
reaction will become 2.(1 M)
(c) Arrhenius equation in terms of k2 and k1 is:
k2 Ea  1 1 
log     (1 M)
k1 2.303R  T1 T2 
31. (a) The rate constant (k) for the first-order decomposition T1 = (25 + 273) K = 298K
of C6H5NH2 can be determined using the integrated T2 = (50 + 273) K = 323K
rate equation: Now, according to the given information.
 [C H NH 2 ]  10k1 Ea  1 1 
ln  6 5   kt log  
 [C6 H5 NH 2 ]0  k1 2.303  8.314  298 323 
Taking the natural logarithm of both sides and using 1 × 2.303 × 8.3 = Ea [2.60 ×10–4]
the data at t = 0 and t = 300 seconds: Ea = 73642.8 J/Mol or 73.642 kJ/mol(1 M)
 0.152 
ln    k  300  (1 M) 32. (a) In octahedral coordination compounds, the d-orbitals

 0 . 3  of the metal ion split into two sets of different energies
ln (0.5067) = –300k due to repulsion from the surrounding ligands. This
effect is known as Crystal Field Splitting.
ln(0.5067)
k  0.0023 s 1 (1 M) t2g set: This set consists of three d-orbitals (dxy, dyz,
300 and dxz) with lower energy. These orbitals experience
(b) The half-life of the reaction can be calculated using relatively less repulsion from the ligands as they point
the first-order half-life equation: between the axes.
eg set: This set comprises two d-orbitals (dx2 – y2 and
t1/ 2  ln(2)  0.693  301.3 dz2) with higher energy. These orbitals experience
k 0.0023
more significant repulsion from the ligands as they
The half-life of the reaction is approximately 301.3 point along the axes directly facing the ligands.
seconds.(1 M)
The energy diagram for the d-orbitals in an octahedral
(c) To find the concentration of C6H5NH2 after 400 complex looks like this: (1 M)
seconds, we can use the integrated rate equation: eg
 [C H NH 2 ]  dx2–y2, dz2
ln  6 5   kt
 [C6 H 6 NH 2 ]0  6Dq or 0.6D0
Taking the natural logarithm of both sides and using D0
the data at t = 0 and t = 400 seconds: Centre of
d-orbitals gravity line
 [C H NH 2 ] 
ln  6 5   0.0023  400  (1 M) (5-fold or barycentre
 0.3  d-orbitals degenerate) –4Dq or –0.4D0
 [C H NH 2 ]  t2g
ln  6 5   0.92 Free ion dxy, dxz, dyz
 0.3  Oh
[C6 H5 NH 2 ] Crystal Field Splitting in Octahedral Complex
 e 0.92  0.398
0.3 (2 M)

Sample Question Paper-1 135

 This Crystal Field Splitting leads to two different The crystal field splitting in a tetrahedral complex is
energy levels for the d-orbitals in octahedral smaller compared to an octahedral complex because
coordination complexes, with the t2g set being lower there are only two-thirds as many ligands, and they
in energy and the eg set being higher in energy. The have a less direct effect on the d orbitals. The relative
energy difference between these sets gives rise to stabilizing effect of the e set is –6Dq (where Dq
Crystal Field Stabilization Energy (CFSE). The represents the crystal field splitting parameter), and
splitting of degenerate d-orbitals in the presence the destabilizing effect of the t2 set is +4Dq.(1 M)
of ligands is referred to as crystal field splitting.
This energy difference between the t2g and eg levels
is represented by “Δo” (where the subscript “o” Nailing the Right Answer
indicates octahedral). The magnitude of Δo depends
on the type of ligands.(1 M) Crystal Field Stabilization Energy (CFSE) in tetrahedral
(b) This type of isomerism arises when an interchange complexes describes the energy difference between
of ligands between cationic and anionic entities the lower energy. e set and the higher energy t2 set of
having different metal ions takes place. Example. d-orbitals due to ligand-metal ion interactions. The CFSE
in [Cr(NH3)6] [Co(CN)6] ligands NH3 and CN can arises from the repulsion between the ligands and specific
interchange between two complexes. (1 M) d-orbitals, leading to a stabilization of the e set and a
destabilization of the t2 set.
OR
(a) In a tetrahedral crystal field, The five fold (b) An ambidentate ligand is a type of ligand that has
degenerate d orbitals of the metal ion split into two two different donor atoms and can link to a metal
energy levels. The representation of these two sets ion through either of them. For instance, the ligands
of orbitals is known as Td. The dx2 – y2 and dz2 orbitals NO2– and SCN– are examples of ambidentate ligands.
experience less repulsion from the ligands compared
On the other hand, a chelating ligand refers to a di-
to the dxy, dyz, and dzx orbitals. As a result, the energy
of the dxy, dyz, and dxz orbitals is raised, while the or polydentate ligand that uses two or more donor
energy of the dx2 – y2 and dz2 orbitals is lowered. atoms simultaneously to bind to a single metal ion.
For example, the oxalate ion and ethane-1,2-diamine
Tetrahedral complexes have four ligands surrounding
are chelating ligands.(1 M)
the metal ion, resulting in a smaller total negative
charge and weaker ligand field as compared 33. (a) 2CH3–CH2–Br + 2 Na
to octahedral complexes with six ligands. The Bromoethane
Dry ethene
direction of the d-orbitals does not coincide with the  CH3–CH2–CH2–CH3 (1 M)
directions of the ligands’ approach to the metal ion Butane
in a tetrahedral coordination which contributes to the (b) CH –CH –Br + NaC≡CH CH3–CH2–C≡CH
3 2
observed energy splitting. (1 M) Sodium Bromoethane
1-Butyne
t2 (1
acetylide M)
dxy, dxz, dyz +
(c) CH3–CH2–Br + Na O C2 H5 C2H5O–C2H5
4 Dq Bromoethane Sodium ethoxyethane
D1
ethoxide
d-orbital (1 M)
C.G line
(5-fold (d) CH3–CH2–CH2–Cl + AgNO2 CH3–CH2–CH2–NO2
d-orbital degenerate) – 6 Dq 1-Chloropropane Silver (1-nitropropane)
e nitrite
dx2–y2, dz2 (1 M)
Free ion Td
Crystal Field Splitting in Tetrahedral Complex SOCl2
(e) CH3–CH2–CH2–OH CH3–CH2–CH2–Cl
(2 M) Propanol 1– Chloropropane
In a tetrahedral coordination compound, the (1 M)
repulsions between the ligands and the metal ion lead alc.
to the splitting of the fivefold degenerate d orbitals (f ) CH3–CH2–CH2–CH2–Br CH3–CH2–CH=CH2
KOH
into two energy levels: Bromobutane But-1-ene
t2 set: This set consists of three orbitals (dxy, dyz, and (1 M)
dxz) with higher energy.
e set: This set comprises two orbitals (dx2 – y2 and dz2) (g) CH3–CH2–Br + NaI CH3–CH2–I  (1 M)
with lower energy. Bromoethane Iodoethane

136 CHEMISTRY – XII P

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