Chapter 11.

The Group 2 Elements:

QS12.3 Use ionic radii to predict a structure type of BeSe?
The ionic radious of Be is 41 pm (coordination number = 4) and the ionic radious of Se is 194
pm. The radius ratio is 41/194 = 0.21. Which according to Table 3.6 suggests that the
…………………………………

Limiting radius Coordinatin shape

ratio r+/r– number
<0.155 2 Linear
0.155 to 0.225 3 Planar triangle
0.225 to 0.414 4 Tetrahedral
0.414 to 0.732 4 Square planar
0.414 to 0.732 6 Octahedral
0.732 to 0.99 8 Body-centred cubic

Doubt: The radius ratio of BeSe is 0.21 but according Table 3.6 this value does not belong to
any given range.
According to above Table (It has been taken from one of the Inorganic Chemistry Books) this
value belongs to (0.155 to 0.225) range but the coordination number of Be does not matching.
So I am not getting correct answer.

Q12.4 Why does Beryllium fluoride form a glass when cooled from a melt?
BeF2 is a glassy solid as it exists in several temperature-dependent phases similar to those of
SiO2.

Q12.7 Which of the salts MgSeO4 or BaSeO4 would be expected to be more soluble in water?
BaSeO4 is more soluble in water. BaSeO 4 is ionic because of the larger radius of Ba 2+ than
Mg2+ where as MgSeO4 is covalent because of a smaller radius and high electron density of
Mg2+
than Ba 2+. Ionic compounds are more soluble in water than the covalent compounds.

Q12.8 Which Group 2 salts are used as drying agents and why?
Anhydrous Mg and Ca sulfates are used as drying agents. This is because of the formation of
hard materials (For example gypsum CaSO 4 . 2H2O and plaster of Paris CaSO4 . 1/2H2O)
after addition of water molecules to these sulfates.

Q12.10 Predict structures for BeTe and BaTe?

Limiting radius Coordinatin shape

ratio r+/r– number
<0.155 2 Linear
0.155 to 0.225 3 Planar triangle
0.225 to 0.414 4 Tetrahedral
0.414 to 0.732 4 Square planar
0.414 to 0.732 6 Octahedral
0.732 to 0.99 8 Body-centred cubic
The ionic radious of Be is 41 pm (coordination number = 4) and the ionic radious of Te is 221
pm. The radius ratio is 41/221 = 0.18. Which according to Table 3.6 suggests that the
…………………………………
Doubt: The radius ratio of BeTe is 0.18 but according Table 3.6 this value does not belong to
any given range.
 According to above Table (It has been taken from one of the Inorganic Chemistry Books) this
value belongs to (0.155 to 0.225) range but the coordination number of Be does not matching.
So I am not getting correct answer.

The ionic radious of Ba is 156 pm (coordination number = 8) and the ionic radious of Te is
221 pm. The radius ratio is 156/221 = 0.70. Which according to Table 3.6 suggests that the
…………………………………
Doubt: The radius ratio of BaTe is 0.70 but according Table 3.6 this value belong to 0.414 to
0.732 but the coordinatin number of Ba does not matching.
According to above Table (It has been taken from one of the Inorganic Chemistry Books) this
value belongs to (0.414 to 0.732) range but the coordination number of Ba does not matching.
So I am not getting correct answer.

Q12.11 Use the data in Table 1.1 and the Ketelaar triangle in Fig. 2.2 to predict the nature of the
bonding in BeBr2, MgBr2, and BaBr2?
The Pauling electronegativity values of Be, Mg, Ba and Br are 1.5, 1.2, 0.9 and 2.8
respectively.
The average electronegativity of BeBr2 is therefore 2.15 and the difference is 1.3. The values
on the Ketelaar triangle indicate that BeBr2 should be covalent.
The average electronegativity of MgBr2 is therefore 2.0 and the difference is 1.6. The values
on the Ketelaar triangle indicate that MgBr2 should also be ionic.
The average electronegativity of BaBr2 is therefore 1.85 and the difference is 1.9. The values
on the Ketelaar triangle indicate that BaBr2 should be ionic

Chapter 12. The Group 13 Elements:

11
QS13.1 B nuclei have I = 3/2. Predict the number of lines and their relative intensities in the
1
H-NMR spectrum of BH4– ?
VSEPR theory predicts that a species with four bonding pairs of electrons should be
tetrahedral.

-
H

B
H H
H
All protons are in equal environment and it gives a quartet by coupling with 11B. Therefore the
number of lines in the 1H-NMR spectrum of BH4– is 4. Their relative intensity ratio is 1:3:3:1.
QS13.2 Write an equation for the reaction of LiBH 4 with propene in ether solvent and a 1:1
stoichiometry and another equation for its reaction with ammonium chloride in THF
with the same stoichiometry?

THF
LiBH4 + NH4Cl BH3NH3 + LiCl + H2
QS13.4 Suggest a reaction or series of reactions for the preparation of N, N’, N”-trimethyl-B,
B’, B”-trimethylborazine starting with methylamine and boron trichloride?

CH3NH2 + HCl CH3NH3Cl

Heat
CH3NH3Cl + BCl3
Cl
H3C B CH3
N N
B B
Cl N Cl
CH3

CH3MgCl

CH3
H3C B CH3
N N
B B
H3C N CH3
CH3

QS13.5 How many framework electron pairs are present in B4H10 and to what structural
category does it belong? Sketch its structure?

The formula B4H10 belongs to a class of borohydrides having the formula B nHn+6, which is
characteristic of a arachno species. Assume one B–H bond per B atom, there are 4 BH units,
which contribute 4x2 = 8 electrons, and the six additional H atoms, which contribute a further
6 electrons, giving 14 electrons, or seven electron pairs which is n+3 with n = 4. This is
characteristic of arachno clusters. The resulting seven pairs are distributed: two are used for
the additional terminal B–H bonds, four are used for the four BHB brides, and one is used for
the central B–B bond.

Q13.3 Arrange the following in order of increasing Lewis acidity: BF 3, BCl3, AlCl3. In the light
of this order, write balanced chemical reactions (or no reaction) for (a) BF 3N(CH3)3 +
BCl3 , (b) BH3CO + BBr3 ?
The order of increasing Lewis acidity is BCl3>BF3>AlCl3.
(a) BF3N(CH3)3 + BCl3 BCl3N(CH3)3 + BF3
(b) BH3CO + BBr3 BH3·solvent + BBr3CO

Q13.7 Predict how many different boron environments would be present in the proton-
decoupled 11B-NMR of a) B5H11, b) B4H10?
 The structure of B5H11 :

Three different boron environments are present in the proton-decoupled 11B-NMR B5H11.
The structure of B4H10 :

Two different boron environments are present in the proton-decoupled 11B-NMR B4H10.
Q13.8 predict the products from the hydroboration of (a) (CH3)2C=CH2 (b) CH CH?
(a) BH3 + (CH3)2C=CH2 B[CH2-CH(CH3)2]3
(b) BH3 + CH CH B(CH=CH2)3

Q13.9 Diborane has been used as rocket propellant. Calculate the energy released from 1.00 kg
of diborane given the following values of : B2H6 = 31, H2O = -242, B2O3 = -1264. The
combustion reaction is B2H6 (g) + 3O2 (g) 3H2O (g) + B2O3 (s). What would be
the problem with diborane as a fuel?
Diborane is an inflammable colourless gas with a sticky sweet odour and is extremely toxic. It
is an extremely reactive gas and hence should be handled in a special apparatus. So that is
comes in contact only with glass and mercury. This is the probable disadvantage for the use of
diborane as a fuel.

Q13.11 Given NaBH4, a hydrocarbon of your choice, and appropriate ancillary reagents and
solvents, give formulas and conditions for the synthesis of (a) B(C 2H5)3, (b) Et3NBH3?

Heat, Ether
(a) BCl3 + 3C2H5MgCl B(C2H5)3 + 3MgCl2

(b) We should expect NaCl, with its high lattice enthalpy, to be a likely product. If this is the
case we shall be left with BH4– and [HN(C2H5)3]+. The interaction of the hydridic BH4– ion
with the protic [HN(C 2H3)5]+ ion will evolve hydrogen to produce triethylamine and BH 3. In
the absence of other Lewis bases, the BH 3 molecule would coordinate to THF, however, the
stronger Lewis base triethylamine is produced in the initial reactions, so the overall reaction
will be

[HN(C2H5)3]Cl + NaBH4 H2 + H3BN(C2H5)3 + NaCl

Q13.12 Draw the B12 unit that is a common motif of boron structures; take a viewpoint along a
C2 axis?

C2-Axis viewpoint of B12

Q13.13 Which boron hydride would you expect to be more thermally stable, B 6H10 or B6H12?
Give a generalization by which the thermal stability of a borane can be judged?

The compounds fall into two classes. B6H10 has the formula BnHn+4 and the other, B6H12,
which is richer in hydrogen and less stable, has the formula B nHn+6. B6H10 is more thermally
stable than B6H12.
Q13.14 How many skeletal electrons are present in B5H9?

The formula B5H9 belongs to a class of borohydrides having the formula B nHn+4, which is
characteristic of a nido species. Assume one B–H bond per B atom, there are 5 BH units,
which contribute 5x2 = 10 electrons, and the four additional H atoms, which contribute a
further 4 electrons, giving 14 electrons, or seven electron pairs which is n+2 with n = 5. This
is characteristic of nido clusters. Total 14 skeletal electrons are present in B5H9.

Q13.15 (a) give a balanced chemical equation (including the state of each reactant and product)
for the air oxidation of pentaborane(9). (b) Describe the probable disadvantages, other
than cost, for the use of pentaborane as a fuel for an internal combustion engine?
Heat
(a) 2B5H9 (l) + 12O2 (g) 5B2O3 (s) + 9H2O (l)
(b) The disadvantage for the use of pentaborane as a fuel is the incomplete combustion to
B2O3. Because of this the exhaust nozzles of the rocket became partly blocked with an
involatile BO polymer.

Q13.16 (a) From its formula, classify B10H14 as closo, nido, or arachno. (b) Use Wade’s rules to
determine the number of framework electron pairs for decaborane(14). (c) Verify by
detailed accounting of valence electrons that the number of cluster valence electrons of
B10H14 is the same as that determined in (b)?

(a)The formula B10H14 belongs to a class of borohydrides having the formula B nHn+4, which is
characteristic of a nido species.
 (b)Assume one B–H bond per B atom, there are 10 BH units, which contribute 10x2 = 20
electrons, and the four additional H atoms, which contribute a further 4 electrons, giving 24
electrons, or 12 electron pairs which is n+2 with n = 10. This is characteristic of nido clusters.
(c) The number of framework electrons in B10H14 are 24. Remaining 10 BH units contain 10x2
= 20 electrons (the B atom provides three electrons and the H atom provides one but, of these
four, two are used for the B-H bond and remaining two are framework electrons). Therefore
the number of cluster valence electrons of B10H14 are 44.
The number of valence electrons in B atom is 3 and in H atom is 1. Therefore the number of
valence electrons in B10H14 is = 10x3 + 14 = 44.
Therefore the number of valence electrons of B10H14 are the same as that determined in (b).

Q13.17 Starting with B10H14 and other reagents of your choice, give the equations for the
synthesis of [Fe(nido-B9C2H11)2]2–, and sketch the structure of this species?

(1) B10H14 + 2SEt2 B10H12(SEt2)2 + H2

(2) B10H12(SEt2)2 + C2H2
(3) 2 B10C2H12 + 2EtO– + 4EtOH
(4) Na[B9C2H12] + NaH
THF
(5) 2Na2[B9C2H11] + FeCl2
B10C2H12 + 2SEt2 + H2
2 B9C2H12– + 2B(OEt)3 + 2H2
Na2[B9C2H11] + H2
2NaCl + Na2[Fe(B9C2H11)2]

H 2-

B
H
H H
B
B B
H H
B B
H
C B H
C B
H H B H
Fe
H B H H
B C
H
B C H
B B H
H
B B
H B H
H
B
H

Chapter 13. The Group 14 Elements:

Q14.3 SiF4 reacts with (CH3)4NF to form [(CH3)4N][SiF5]. (a) Use the VSEPR rules to
determine the shape of the cation and anion in the product; (b) Account for the fact that
the 19F NMR spectrum shows two fluorine environments?
(a) The cation is [(CH3)4N]+
The number of electrons present on central N atom = 8
the number of electron pairs = 4
 Therefore the shape of the cation is tetrahedral.
+
CH3

N
H3C CH3
C
H3
The anion is SiF5–
The number of electrons present on central Si atom = 4+5+1=10
the number of electron pairs = 5

-
Therefore the shape of the anion is trigonal bipyramid.

Si F

F
(b) In the structure of anion there are two different fluorine environments. One is equatorial
fluorine atoms and other one is axial fluorine atoms

Q14.4 Draw the structure and determine the charge on the cyclic anion [Si4O12]n–?
 O

Si
O O

O Si
Si O

O O
Si

O
The general formula of silicates is (SiO3)n2n–
If n = 4 then 2n = 8. Therefore the charge on the cyclic anion [Si4O12]n– = –8.

Q14.5 Predict the appearance of the 119Sn-NMR spectrum of Sn(CH3)4?

119 119
Sn-NMR spectrum of Sn(CH3)4 contains doublet peak of Sn ( I = ½) nucleus by coupling
with 12 equivalent protons.

Q14.6 Predict the appearance of the 1H-NMR spectrum of Sn(CH3)4?

1
H-NMR spectrum of Sn(CH3)4 contains doublet peak of 1H ( I = ½) nucleus by coupling with
119
Sn (I = ½) nucleus.

Q14.7 Use the data in Table 14.2 and the additional bond enthalpy data given here to calculate
the enthalpy of hydrolysis of CCl 4 and CBr4. Bond enthalpies/(kj mol–1): O–H = 463, H–
Cl = 431, H–Br = 366?

The enthalpy of hydrolysis of a compound can be calculated as the difference in energy

between the bonds broken and the bonds formed in the hydrolysis reaction. Therefore, the
relevant equations for the hydrolysis of CCl4 and CBr4.
CCl4 (l) + 2H2O (l) CO2 (g) + 4HCl (aq)
ΔhH˚CCl4 = [(2x743) + (4x431)] – [(4x322) + 2(2x463)]
= [1526 + 1724] – [1288 + 2x926]
= 3250 – [1288 +1852]
= 3250 – 3140
= 110 kjmol–1

CBr4 (l) + 2H2O (l) CO2 (g) + 4HBr (aq)

ΔhH˚CBr4 = [(2x743) + (4x366)] – [(4x288) + 2(2x463)]

= [1526 + 1464] – [1152 + 2x926]
= 3090 – [1152 +1852]
= 3090 –. 3004
= 86 kjmol–1

Q14.12 (a) Describe the trend in band gap energy, Eg, for the elements carbon (diamond) to tic
(grey), (b) Does the electrical conductivity of silicon increase or decrease when its
temperature is changed from 20˚C to 40˚C?
 Elements Bond gap energy (Eg)
C (diamond) 5.5
Si 1.11
Ge 0.67
Sn no bond gap

There is decrease in band gap energy from carbon to tin. This because the trend of non-metal
to metal character of these elements. The electrical conductivity of silicon increase with
increased temperature (20˚C to 40˚C) because the amplitude of atomic vibrations increase and
it leads to increase in interatomic spacing.

Q14.13 Preferably without consulting reference material, draw a periodic table and indicate the
elements that form saline, metallic, and metalloid carbides?

Ionic(silane) Metallic carbides Metalloid

carbides carbides
Group I Li, Na, K, Rb, Cs
elements
Group II Be, Mg, Ca, Sr,
elements Ba
Group 13 Al B
elements
Group 14 Si
elements
3d-Block Sc, Ti, V, Cr, Mn, Fe,
elements Co, Ni
4d-Block Zr, Nb, Mo, Tc, Ru
elements
5d-Block La, Hf, Ta, W, Re, Os
elements
6d-Block Ac
elements
Lanthanides Ce, Pr, Nd, Pm, Sm,
Eu, Gd, Tb, Dy, Ho,
Er, Tm, Yb, Lu

Chapter 14. The Group 15 Elements:

Q15.4 Show with an equation why aqueous solutions of NH4NO3 are acidic?
NH4NO3 NH4+ + NO3–
strong weak
conjugate acid conjugate base
The aqueous solution of NH4NO3 contains NH4+ ions and NO3– ions. NH4+ ions are strong
conjugate acids whereas NO3– ions are weak conjugate bases. Due to the domination of strong
acidic nature of NH4+, the aqueous solution of NH4NO3 are acidic.
Stronger acid, HNO3, has the weaker conjugate base (NO3–)
HNO3 H+ + NO3–
(SA) (WCB)
Weaker base, NH4OH, has the stronger conjugate acid (NH4+)
NH4OH NH4+ + OH–
(WB) (SCA)
Q15.5 Carbon monoxide is a good ligand and is toxic. Why is the isoelectronic N 2 molecule not
toxic?
CO is toxic because it forms a complex with haemoglobin in the blood, and this complex is
more stable than oxy-haemoglobin. This prevents the haemoglobin in the red blood corpuscles
from carrying oxygen round the body. This causes an oxygen deficiency, leading to
unconsciousness and then death.
N2 itself, with a triple bond between the two atoms, is strikingly unreactive. The unreactivity
of N2 appears to be the result of several factors. One is the strength of the N–N triple bond.
Second one is the relatively large size of the HOMO – LUMO gap in N 2. A third factor is the
low polarizability of N2. So that N2 can not form complex with haemoglobin in the blood.
Therefore, N2 molecule not toxic.

Q15.6 Compare and contrast the formulas and stabilities of the oxidation state of the common
nitrogen chlorides with the phosphorus chlorides?
Trihalides of nitrogen are the least stable. NCl 3 is explosive. Due to Pauling’s
electronegativity of nitrogen (3.0) and chlorine (3.0) are the same and the N–Cl bond is
almost nonpolar. Therefore nitrogen trichloride is covalent in nature. Whereas PCl 3 is the
most important and stable trichloride of phosphorus. Due to Pauling’s electronegativity of
phosphorus (2.1) is lesser than the Pauling’s electronegativity of chlorine (3.0). Therefore
phosphorus shows +III oxidation state in it trichloride.
Nitrogen is unable to form pentachloride because the second shell contains a maximum of
eight electrons i.e. four bonds. The subsequent element phosphorus has suitable d orbitals,and
form the stable pentachloride. In phosphorus (PCl5) pentachloride, the oxidation state of P
atom is +IV.

Chapter 15. The Group 16 Elements:

QS16.1 Determine whether the decomposition of H 2O2 is spontaneous in the presence of either
Br– or Cl–?
In Presence of Br–
1). Br2 (aq) + H2O2 (aq) 2Br– (aq) + O2 (g) + 2H+ (aq)
– +
2). 2Br (aq) + H2O2 (aq) + 2H (aq) Br2 + 2H2O (l)
So the net reaction is simply the decomposition of H2O2.
3). 2H2O2 O2 (g) + 2H2O (l)
The first reaction is the difference between the half reactions
Br2 + 2e– 2Br– Eө = +1.06 V
+ –
O2 (g) + 2H + 2e H2O2 Eө = +0.70 V
ө
And therrefore E cell + + 0.36 V. This reaction is therefore spontaneous.
The second reaction is the difference between the half reactions
H2O2 (aq) + 2H+ (aq) + 2e– 2H2O (l) Eө = +1.77 V
– –
Br2 + 2e 2Br Eө = +1.06 V
ө
And therrefore E cell = + 0.71 V. This reaction is therefore spontaneous. Because of both
reactions are spontaneous, the decomposition of H2O2 is thermodynamically favored in
presence of Br–.
In Presence of Cl–
1). Cl2 (aq) + H2O2 (aq) 2Cl– (aq) + O2 (g) + 2H+ (aq)
– +
2). 2Cl (aq) + H2O2 (aq) + 2H (aq) Cl2 + 2H2O (l)
So the net reaction is simply the decomposition of H2O2.
3). 2H2O2 O2 (g) + 2H2O (l)
The first reaction is the difference between the half reactions
Cl2 + 2e– 2Cl– Eө = +1.36 V
O2 (g) + 2H+ + 2e– H2O2 Eө = +0.70 V
ө
And therrefore E cell + + 0.66 V. This reaction is therefore spontaneous.
 The second reaction is the difference between the half reactions
H2O2 (aq) + 2H+ (aq) + 2e– 2H2O (l) Eө = +1.77 V
– –
Cl2 + 2e 2Cl Eө = +1.36 V
ө
And therrefore E cell = + 0.41 V. This reaction is therefore spontaneous. Because of both
reactions are spontaneous, the decomposition of H2O2 is thermodynamically favored in
presence of Cl–.

Q16.6 Predict which oxidation states of Mn will be reduced by sulfite ions in basic conditions?

Q16.9 Use the standard potential data in Resource section 3 to predict whether SeO 32– is more
stable in acidic or basic solution?

Chapter 16. The Group 17 Elements:

QS17.2 Predict the 19F-NMR pattern for IF7?
The 19F-NMR spectrum of IF7 contains two resonances to integrate seven fluorine atoms. One
sextet is for axial 2F atoms and another triplet is for 5equatorial F atoms.

Q17.5 Which dihalogens are thermodynamically capable of oxidizing H2O to O2?

The oxidation potential of different dihalogens and H2O
2I– I2 + 2e– EөI–/I2 = –0.53 V
– –
2Br Br2 + 2e EөBr–/Br2 = –1.06 V
– –
2Cl Cl2 + 2e EөCl–/Cl2 = –1.36 V
– –
2F F2 + 2e EөF–/F2 = –2.85 V
+ –
2H2O O2 (g) + 2H + 4e EөH2O/O2 = –1.23 V

The oxidation potential of I2 and Br2 are higher than the oxidation potential of H 2O and the
oxidation potential of Cl2 and F2 are lower than the oxidation potential of H 2O. Therefore Cl2
and F2 are thermodynamically capable of oxidizing H2O to O2

Q17.8 Given that 1.84 g of IF3 reacts with 0.93 g of [(CH3)4N]F to form a product X, (a) identify
X, (b) use the VSEPR model to predict the shapes of IF 3 and the cation and anion in X,
(c) predict how many 19F-NMR signals would be observed in IF3 and X?

a). IF3 + [(CH3)4N]F IF4N(CH3)4

(10 mmol) (10 mmol) (10 mmol)

Therefore X = IF4N(CH3)4
b). The shape of IF3 is T-shape.
 F

I F

F
The shape of anion IF4– is Sqare planar.

.. -
F F
I
F F
..
The shape of cation (CH3)4N+ is Tetrahedral.

+
CH3

N
H3C CH3
C
H3
c).The 19F-NMR spectrum of IF3 contains two resonances to integrate three F atoms. One
doublet is for axial 2F atoms and another triplet is for 1equatorial F atom.
The 19F-NMR spectrum of IF4– contains one resonance to integrate four fluorine atoms. One
singlet is assigned for four equivalent F atoms.

Q17.13 Predict the shape of the doubly chlorine-bridged I2Cl6 molecule by using the VSEPR
model and assign the point group?

I2Cl6 is the dimer of ICl3 and in this molecule 2Cl are bridged atoms. Therefore each I atom
contains 12 valence electrons, or 4 bonding pairs and 2 non-bonding pairs. VSEPR theory
predicts that the shape around each I atom with 6 pairs of electrons should be octahedral. In
this structure 4 Cl atoms occupy the corners of square plane in octahedral geometry.
Therefore in the solid state it is present as a planar dimer I2Cl6 with bridging Cl atoms.
 Cl Cl Cl
I I
Cl Cl Cl
The point group of I2Cl6 is D2h.

Q17.14 Predict the structure and identify the point group of ClO2F?

ClO2F is pyramidal molecule.

O
Cl F
O
This molecule belongs to Cs point group.

Q17.16 Predict the appearance of the 19F-NMR spectrum of IF5+?

VSEPR theory predicts that a species with five bonding pairs of electrons should be trigonal
bipyramidal.

+
F

I F

F
The 19F-NMR spectrum of IF5+ contains two resonances to integrate five F atoms. One quartet
is for equatorial 3F atoms and another triplet is for axial 2F atom.