PMT

1 The elements silicon, phosphorus and sulfur are in Period 3 of the Periodic Table.

(a) (i) Describe the variation in atomic radius from silicon to sulfur.

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(ii) The melting point of silicon is 1410 °C. The melting point of sulfur is 113 °C.

Explain this difference.

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(b) Table 1.1 shows some properties of the elements Si to S.

The first ionisation energy of P is not shown.

Table 1.1

property Si P S
total number of electrons in s subshells
total number of electrons in p subshells
first ionisation energy / kJ mol–1 786 1000
formula of most common chloride SiCl 4 PCl 5 SCl 2

(i) Complete Table 1.1 to show the total number of s and p electrons in an atom of Si, P
and S.
[2]

(ii) Construct an equation to represent the first ionisation energy of Si.

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(iii) Three possible values for the first ionisation energy of P are given.

619 kJ mol–1 893 kJ mol–1 1060 kJ mol–1

Circle the correct value.

Explain your choice, including a comparison of your chosen value to those of Si and S.

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(iv) SiCl 4 and PCl 5 each react with water, forming misty fumes.

Identify the chemical responsible for the misty fumes.

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(v) Predict the shape of the SCl 2 molecule.

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2 NO and NO2 react at 25 °C to give N2O3 as shown in the equation.

NO(g) + NO2(g) N2O3(g) ΔH = –7.2 kJ mol–1

The reaction is reversible and reaches equilibrium in a closed system.

(a) Fig. 2.1 shows how the rate of the forward reaction changes with time.

Initially, the rate of the reverse reaction is zero.

Complete Fig. 2.1 to sketch how the rate of the reverse reaction changes with time.

rate of
reaction

time

Fig. 2.1
[1]

(b) State how the position of equilibrium changes, if at all, when the reaction takes place at
100 °C.

Explain your answer.

Assume the pressure remains constant.

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(c) Table 2.1 shows the composition of an equilibrium mixture of NO(g), NO2(g) and N2O3(g) at
101 kPa.

Table 2.1

number of moles at
gas
equilibrium / mol
NO 0.605
NO2 0.605
N2O3 0.390

Calculate Kp , the equilibrium constant with respect to partial pressures.

Deduce the units of Kp.

Kp = ..................................... units .......................................

[3]

(d) Identify one natural process and one man-made process that cause the formation of
atmospheric NO and NO2.

natural process .........................................................................................................................

man-made process ....................................................................................................................

[2]

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(e) NO2 is a brown gas that can be used to form nitric acid.

(i) NO2 is a free radical.

Define free radical.

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(ii) NO2 has a catalytic role in the oxidation of atmospheric sulfur dioxide.

Write equations to show the catalytic role of NO2 in this oxidation.

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(iii) State one environmental consequence of the oxidation of atmospheric sulfur dioxide.

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(f) A student titrates nitric acid with a base to form a solution containing aqueous magnesium
nitrate.

(i) Identify a base that the student could use.

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(ii) The student evaporates the water to obtain magnesium nitrate solid. When this solid is
heated it decomposes.

Write an equation for the decomposition of magnesium nitrate.

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(iii) State how the thermal stability of Group 2 nitrates changes down the group.

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[Total: 15]

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3 Phosphoric(V) acid, H3PO4, is used in both inorganic and organic reactions.

(a) H3PO4 is made in a two-step process from phosphorus.

step 1 Phosphorus reacts with an excess of oxygen to form a white solid.

step 2 The white solid then reacts with water to form H3PO4.

(i) Write an equation for each step.

step 1 ................................................................................................................................

step 2 ................................................................................................................................
[2]

(ii) H3PO4 is a weak Brønsted–Lowry acid.

Define weak Brønsted–Lowry acid.

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(b) H3PO4 is also formed in the process shown in reaction 1.

reaction 1 4H3PO3 3H3PO4 + PH3

Table 3.1 shows some relevant thermodynamic data.

Table 3.1

enthalpy change of formation,

compound
ΔHf / kJ mol–1
H3PO3 –972
H3PO4 –1281
PH3 +9

(i) Define enthalpy change of formation.

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(ii) Use the data in Table 3.1 to calculate the enthalpy change, ΔH r , of reaction 1.

ΔH r = ................................................. kJ mol–1
[2]

(iii) Explain why reaction 1 is a disproportionation reaction.

Explain your reasoning with reference to relevant oxidation numbers.

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