Chemistry unit 4

1. D
2. A
3. C
4. (a) C
(b) A
(c) C (methyl orange, bromophenol blue, bromocresol green)
5. D
6. D
7. C
8. (a) C
(b) B
(c) B
9. (a) A
(b)B
10. D
11. (a) D
(b) A
12. C
13. C
14. D ?
∆𝐻 −25.7 𝑥 1000
15. (a) ∆Ssurroundings= - 𝑇
= 298
= -86.2 J K-1 mol-1
??(b) ∆Ssystem is positive. When NH4NO3 dissolves in water, free ions are produced which
increase the value of ∆Ssystem. So, its value is is higher than that of ∆Ssurroundings.
16. (a) (i) Plot graph using the points given, rate on the y axis, conc on the x axis.
(ii) Rate vs. concentration graph for BrO3- is a straight line through the origin. So, it is first
order with respect to BrO3- ions.
(b) (i) Br- : 1st order
H+ : 2nd order
(ii) Rate = K [BrO3-] [Br-] [H+]2
(iii) 1.52 = K x 0.062 x 0.21 x 0.42
K= 7.30 x 10-3 mol-3dm9 s-1
(c) Solid heterogeneous catalysts,such as palladium, adsorbs BrO3- ions onto active sites
on the catalyst surface. The active site increases proximity of the molecule by providing
a larger surface area and weakens covalent bonds, thus increasing rate of the reaction.
66,7
17. (a) mol(C) = 12
= 5.558
11.1
mol(H) = 1
= 11.1
22.2
mol(O) = 16
= 1.3878
C:H:O = 5.558 : 11.1 : 1.3878 = 4 :8 : 1
So, the empirical formula is C4H8O and the molecular formula is double of that, so 2
(C4H8O) is C8H16O2.
 (b) (i) 2,2- dimethylpropyl propanoate
(ii) C2H5COOH and C(CH3)3OH
(c) (i) B is the CH2 beside A, C is the CH 2 beside the O and the rest is D.
(ii) B : quartet, 2 ; C : singlet,2 ; D : singlet,9
18. Both NaCl and MgI2 are ionic, so show ionic bonding. But, according to the table, there is
a large difference in theoretical and experimental lattice energy for MgI2 compared to
NaCl. So MgI2 will have more covalent character than NaCl. This is because Mg2+ ion
has a larger charge than Na+ ion, so the Mg2+ ion has higher polarising power. On the
other hand, the I- ion is larger than the Cl- ion, so the I- ion is more likely to be polarised.
The combination of the effects causes more distortion for MgI2 than for NaCl, thus giving
it more covalent character.
The bond strength is higher for NaCl than MgCl2 because it is less polarised and has
more ionic character than MgCl2.
19. (a) (i) Nucleophilic substitution mechanism
(ii) The prediction is incorrect because -CN attacks 𝛿+ carbon of planar ethanal either
above or below the plane of the molecule to obtain equal parts of two optical isomers, or
a racemic mixture, which cannot rotate the plane of plane-polarised light as rotation as
rotation caused by one isomer cancels rotation by other isomer.
(iii) Acid hydrolysis ; Dilute H 2SO4 (aq), H2O ; Heat under reflux ;
CH3CH(OH)CN + 2H2O + H+ →CH3CH(OH)COOH + NH3
(b) NaHCO3 + CH3CH(OH)COOH → CH3COONa + CO2 + H2O
(c) (i) When the concentration of H+ ions increases, equilibrium 1 shifts to the forward
direction which forms carbonic acid and removes the excess H+ ions from the blood,
which restores the original pH. This increases the concentration of carbonic acid and so
equilibrium 2 shifts to the forward direction, causing the carbonic acid to dissociate into
CO2 and H2O, and the CO2 is then removed from the body through the lungs, thus
restoring both equilibriums.
(ii) pH = 7.41
=) -log ( [H+] ) = 7.41
=) [H+] = 10-7.41 = 3.89 x 10-8
[𝐻𝐶𝑂3−] [𝐻+]
Ka = [𝐻2𝐶𝑂3]
[𝐻𝐶𝑂3−] [𝐻+]
=) 4.50 x 10-7 = [𝐻2𝐶𝑂3]
[𝐻𝐶𝑂3−]]
=) [𝐻2𝐶𝑂3]
= (4.50 x 10-7) / (3.89 x 10-8) = 11.564
So, [HCO3-] : [H2CO3] = 11.6 : 1
20. (a) (i) Equilibrium shifts to the forward direction as there are more moles on the reactant
side than the product side. This increases the yield of Cl2 but the value of Kp remains
constant.
(ii) Equilibrium shifts to the backward direction as the reaction is exothermic. This
decreases the yield of Cl2 and decreases the value of Kp.
(iii) Catalyst does not shift the equilibrium as it increases the rate of reaction equally for
both forward and backward reactions.So the yield of Cl2 remains the same and the value
of Kp also remains the same.
(b) (i) Equilibrium moles : 0.350; 0.475; 0.250; 0.250; Total moles : 1.325; Mole fraction :
0.264; 0.358; 0.189; 0.189
(ii) Kp = { (PH2O)2 x (PCl2)2 } / { (PHCl)4 x (PO2) }
(iii) PH2O = 0.189 x 1.5 = 0.2835
PCl2 = 0.189 x 1.5 = 0.2835
PO2 = 0.358 x 1.5 = 0.5370
PHCl = 0.264 x 1.5 = 0.3960
Kp = ( 0.28352 x 0.28352) / (0.39604 x 0.5370) = 0.489 atm-1.
(iv) ∆Stotal = R ln(K) = 8.31 x ln(0.489) = -5.94 J K-1 mol-1.
(c)