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CHEMISTRY

Topic 12B Lattice Energry Grade 12 GCE


Haber Cycle AOUDI TAREK

Name : .................................................................. Grade 12 ..................

Worksheet 1
1. Identify each of the following enthalpy changes:

(a) 2K+(g) + O2(g) 


 K2O(s)

(b) 2K(s) + O2(g) 


 K2O(s)

(c) K(s) 
 K(g)

(d) Ca(g) 
 Ca2+(g)

(e) Cl2(g) 
 2Cl(g)

(f) ½ O2(g) 
 O(g)

(g) O2(g) 
 2O(g)

(h) O(g) 
 O2(g)

(i) K(s) + ½ Cl2(g) 


 KCl(s)

(j) Sr2+(s) + 2Cl(g) 


 SrCl2(s)

2. Write equations for each of the following

(a) Lattice enthalpy of calcium fluoride CaF2 : ……………………………………...…

(b) Enthalpy of formation of CaF2 : ……………………………………………………

(c) atomisation of magnesium : ………………………………………………………...

(d) 1st ionisation of aluminium:………………………………………………………….

(e) sum of 1st , 2nd and 3rd ionisation of aluminum :…………………………………….

(f) 2nd electron affinity of oxygen: …………………………………………………….

(g) lattice enthalpy of sodium oxide Na2O: …………………….………………………

(h) Enthalpy of formation of barium iodide: …………………….……………………

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 1


3. The Born-Haber cycle below represents the enthalpy changes when calcium hydride,
CaH2, is formed from its elements.

Ca2+(g) + 2H+(g)
Identify
H5
H1 ……………………………
Ca2+(g) + 2e + 2H(g) H2 ……………………………
H4
H3 ……………………………

Ca2+(g) + 2e + H2(g) H4 ……………………………


H6
H5 ……………………………
H3
H6 ……………………………
Ca(g) + H2(g)

H2

Ca(s) + H2(g)

H1
CaH2(s)

(a) Write down in terms of one of the symbols ΔH1 to ΔH6


(i) the lattice energy of calcium hydride ........................................................................... [1]
(ii) the first electron affinity of hydrogen ...........................................................................[1]
Ans :½ ΔH5
(b) Use the data below to calculate the standard enthalpy of formation of calcium
hydride,CaH2(s).
/ kJ mol–1
enthalpy of atomisation of calcium +178
first plus second ionisation energies of calcium +1735
enthalpy of atomisation of hydrogen +218
first electron affinity of hydrogen –73
lattice energy of calcium hydride –2389
Ans: −186 kJ mol1
(c) Explain why the lattice energy of magnesium hydride, MgH2(s), is more exothermic
than the lattice energy of calcium hydride, CaH2(s). (3)

The sum of the ionic radii in MgH2 is smaller than in CaH2 but charges the same
so there is a stronger (forces of) electrostatic attraction between ions in MgH2

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 2


4. The lattice enthalpy of calcium chloride, CaCl2 is –2258 kJ mol-1. Explain why this is
more exothermic (less negative) than that of the value for potassium chloride ,
KCl –702 kJ mol-1

Answer

There is an increased electrostatic attraction in CaCl2 due to :


o higher charge of calcium ion Ca2+ relative to potassium ion K+
o smaller size of calcium ion Ca2+ relative to potassium ion

5. (a) Define the term lattice energy.

........................................................................

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

(b) A Born–Haber cycle for the formation of lithium chloride is shown below.

Li + (g) + e – + Cl(g)

Li +(g) + Cl – (g)
Li + (g) + e – + 12 Cl 2 (g)

1
Li(g) + 2 Cl 2 (g) Hlatt

Ha
1
Li(s) + 2 Cl 2 (g)

LiCl(s)

Enthalpy change
/kJ mol–1
Enthalpy of formation of lithium chloride(s) –409
Enthalpy of atomisation of lithium +161
Enthalpy of atomisation of chlorine +122

1st ionisation energy of lithium +519

Electron affinity of chlorine –349

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 3


(i) Calculate the lattice energy, Hlatt, of lithium chloride.

Ans : − 862 kJ mol–1


(2)

(ii) The enthalpy change Ha is the enthalpy of atomisation of lithium metal.

Suggest, and explain, whether you would expect the value of Ha for potassium to
be more or less endothermic than that for lithium.

...................................................................

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

(c) (i) State TWO properties of ions that affect the value for the lattice energy of ionic
compounds.

...................................................................

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

(ii) The calculated value for the lattice energy of potassium chloride is almost exactly
the same value as that found experimentally.

Why is the theoretical value for the lattice energy of silver chloride, –833 kJ mol–1,
so different from the experimentally determined value of –905 kJ mol–l? [2]

The polarisation of anions by cations leads to some covalency in an ionic bond.


There is some covalent character or ”not 100 % ionic” in AgCl /
“AgCl is not purely ionic” .

Which is due to polarisation (distortion) of anion by the Ag+ cation which is


highly polarising.

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 4


6. The formation of magnesium chloride from magnesium and chlorine may be represented by the
following Born-Haber cycle:

Mg 2+(g) + 2Cl(g) + 2e –

Mg 2+(g) + Cl 2 (g) + 2e – Mg 2+ (g) + 2Cl– (g)

Mg(g) + Cl 2 (g)

Mg(s) + Cl 2 (g)

MgCl 2 (s)
(a) Define the term:
Enthalpy of atomisation. (2)

Is the heat energy change for the formation of ONE mole of gaseous
atoms from its element in its standard state.

(b) (i) Identify on the diagram the chance representing the enthalpy of atomisation of
magnesium.
(1)
(ii) Use the data below to calculate the first electron affinity of chlorine.

Value of the enthalpy


Enthalpy change
change / kJ mol–1
Enthalpy of atomisation of magnesium +148
1st ionisation energy of magnesium +738
nd
2 ionisation energy of magnesium +1451
Enthalpy of formation of magnesium chloride –641
Enthalpy of atomisation of chlorine +122
Lattice enthalpy of magnesium chloride
–2526

– 348 kJ mol–1

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 5


7. (a) Electron affinities of an element, such as iodine, can be calculated using a Born-
Haber cycle.

Value / kJ mol–1
Enthalpy of atomisation of calcium, ∆Ha(calcium) +193
1st ionisation energy of calcium, I.E1 +590
2nd ionisation energy of calcium, I.E2 +1150
Enthalpy of atomisation of iodine, ∆Ha(iodine) +107
Lattice energy of calcium iodide, ∆Hlatt –2074
Enthalpy of formation of calcium iodide, ∆Hf –534

(i) Define the term first electron affinity, EA1.


...................................................................

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

(ii) Write suitable symbols or values in the boxes to label the Born-Haber cycle below.

Ca(s) + 2I(g)

Ca(s) + e + 2I(g)

Ca(s) + 2I(g)

Ca(s) + I2(s) CaI2(s)

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 6


(iii) Use the data to calculate the first electron affinity of iodine, EA1.

(2)
Ans : –303.5 kJ mol–1

(b) The values of the lattice energies of potassium iodide and calcium iodide
experimentally determined from Born-Haber cycles and theoretically calculated
from an ionic model are shown below.

Experimental lattice Theoretical


energy lattice energy
/kJ mol–1 /kJ mol–1
Potassium iodide, KI(s) – 651 – 636
Calcium iodide, CaI2(s) –2074 –1905

(i) Explain why the experimental lattice energy of potassium iodide is less
exothermic than the experimental lattice energy of calcium iodide.

...................................................................

...................................................................

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [3]

(ii) Explain why the experimental and theoretical values of the lattice energy are
almost the same for potassium iodide, but are significantly different for
calcium iodide.

...................................................................

...................................................................

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [3]

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 7


8. (a) A Born-Haber cycle for the formation of calcium oxide is shown below.

Ca2+ (g) + O 2–(g)

H5
Ca 2+ (g) + O(g) + 2e –

H4
2+ –
Ca (g) + ½ O 2 (g) + 2e

H3 H6
+ –
Ca (g) + ½ O 2 (g) + e

H2
Ca(g) + ½ O 2 (g)

H1
Ca(s) + ½ O 2 (g)

H7

CaO(s)

Data H/kJ mol –1 :

H1 = +193; H2= 590; H3 = +1150; H4 = +248; H6 = –3513; H7 = –635.

(i) Identify the change which represents the lattice enthalpy of CaO.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [1]

(ii) Use the data above to calculate H5

Ans : H5 = +697 kJ mol–1


(3)
(iii) Use this value of H5 to calculate the first electron affinity of oxygen, given
that the second electron affinity of oxygen is +844 kJ mol–1
(2)

Ans : 1st E.A. = –147 kJ mol–1

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 8


(b) (i) What enthalpy change does the value of H2 represent?

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [3]

(ii) Would the value of H2 be larger or smaller for magnesium than it is for calcium?

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [3]

(iii) Explain your answer in (b)(ii)

...................................................................

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

9. The calculated value of L.E of rubidium chloride RbCl is 674 KJmol –1 ; It is very
similar to the experiment value 676 KJmol –1. Give a reason for the similarity.

Ans:
For ionic compounds the result of exp. Hlatt is the same as the result from the calculated.

10. Explain why does the lattice enthalpy of the chlorides of Group I becomes less exothermic as
the group is descended ?

Answer

Hlatt becomes less exothermic (decreases in magnitude) from NaCl to CsCl since there is a
decreased electrostatic attraction due to:

- Cation size increases from Na+ to Cs+ ion


- Decreasing charge density from Na+ to Cs+ ion

The larger the sum of the ionic radii, the more distance there is between them, and the
weaker the electrostatic forces holding them together.

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 9


11. The Born-Haber cycle for the formation of sodium chloride is shown below:

Na(s) + ½ Cl2(g) H = 411KJ mol–1 NaCl(s)

Na(g) Cl(g)

Na+(g) + Cl(g)

Use the above diagram and the following data to calculate H for the reaction
Cl(g) + e 
 Cl(g)
Na(s) 
 Na(g) H = 107 kJ mol–1
Na (g) 
 Na+(g) H = 496 kJ mol–1
½ Cl2(g) 
 Cl(g) H = 122 kJ mol–1
NaCl(s) 
 Na+(g) + Cl(g) H = +780 kJ mol–1

12. The Born-Haber cycle for the formation of calcium chloride is shown below:

E
Ca2+(g) + 2Cl(g) CaCl2(s)

B D

F
Ca(g) + 2Cl(g)

A C

Ca(s) + Cl2(g)

A = 177 kJ mol–1 B = 1690 kJ mol–1 C= 242 kJ mol–1


E =  2197 kJ mol–1 F =  795 kJ mol–1

(a) A is the enthalpy of sublimation (atomisation) of solid calcium. Similarly


identify the following:
(i) B (ii) C (iii) E (iv) F

(b) Calculate the enthalpy change D

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 10


13. The Born Haber cycle for MgO is shown below:

Mg2+(g) + O2(g)
Identify
H4
H1 ……………………………
Mg2+(g) + 2e + O(g) H2 ……………………………
H3 H3 ……………………………

Mg(g) + O(g) H4 ……………………………


H5
H5 ……………………………
H2
H6 ……………………………
Mg(g) + ½ O2(g)

H1

Mg(s) + ½ O2(g)

H6
MgO(s)

(b) MgO(s) has the same crystal structure as NaCl(s). The lattice enthalpy of NaCl(s) is
–771kJmol–1 whilst that of MgO(s) is –3889 kJ mol–1.
Explain the difference in lattice enthalpies. (4)

In MgO, the two doubly charged ions Mg2+ and O2 would have stronger electrostatic
attraction than in NaCl.

The sum of the ionic radii (distance) between Mg2+ and O2 is smaller than that between
Na+ and Cl. Thus there will be stronger electrostatic forces holding Mg2+ and O2 together.

 this leads to stronger forces of attraction in MgO than in NaCl.

or

Lattice enthalpy depends upon sizes and charges of the ions.

Mg2+ is smaller and doubly charged

Oxide ion O2 is also smaller and doubly charged

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 11


14. Construct Born–Haber cycles for MgCl, MgCl2 and MgCl3, inserting all the values
except Hf.
Since experimentally determined lattice energies for MgCl and MgCl3 are not available,
use the theoretically calculated values:

value
/ kJ mol–1 / kJ mol–1
Mg(s) 
 Mg(g) + 150 Hlatt.[MgCl]  753
Mg(g) 
 Mg+(g) + 740 Hlatt.[MgCl2]  2490
Mg+(g) 
 Mg2+(g) + 1500 Hlatt.[MgCl3]  5450
Mg2+(g) 
 Mg3+(g) + 7700
½Cl2(g) 
 Cl(g) + 122
Cl(g)  Cl(g)
  365

(b) Use the cycles to obtain values for


(i) H f [MgCl] (ii) H f [MgCl2] (iii) H f [MgCl3]

Use the heats of formation to explain which ionic compound exits?

(c) Which of the three compounds MgCl, MgCl2 , MgCl3 is /are energetically stable
with respect to the elements?

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 12


15. Construct Born–Haber cycles for CaF, CaF2 and CaF3, inserting all the values
except Hf.

(b) Use the cycles to obtain values for


(i) H f [CaF] (ii) H f [CaF2] (iii) H f [CaF3]
value
/ kJ mol–1 / kJ mol–1
Ca(s) 
 Ca(g) + 180 Hlatt.[CaF]  798
Ca(g) 
 Ca+(g) + 590 Hlatt.[CaF2]  2580
Ca+(g) 
 Ca2+(g) + 1140 Hlatt.[CaF3]  5400
Ca2+(g) 
 Ca3+(g) + 4940
½F2(g) 
 F(g) + 80
F(g)  F(g)
 335

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 13


16. Using the following data, construct a Born-Haber cycle for potassium chloride and use it
to find the electron affinity of chlorine.
 H / kJ mol–1

o First ionisation energy of potassium +419

o Enthalpy of atomisation of potassium +89

o Enthalpy of atomisation of chlorine +122

o Enthalpy of formation of potassium chloride –437

o Lattice enthalpy of potassium chloride –711

Ans: 356 kJ mol –1


must be negative

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 14


Lattice enthalpy to be expressed as the enthalpy change for the process

M+ (g) + X (g)  


 1 M+X  (s)
gaseous ions 1 mol of ionic solid is formed from
gaseous ions

o The L.E corresponds to the strength of the ionic bond in an ionic solid.
o L.E is always exothermic
o L.E is difficult be to determine or measure directly. So it found either by Born-Haber
cycles or Enthalpy level diagram [ i.e an application of Hess's Law ].
o The larger the negative value of L.E i.e. the more exothermic the process, the more
stable is the lattice being formed.
Ions in gaseous
state
affinities
L.E
Ionisations

atomisations

Elements in their Ho Ionic compound as


standard states formation crystal lattice

Route 1

Ho formation = heats of ( atomisations + ionisations + electron affinities) + L.E

The forces holding an ionic crystal are Columbic


o Factors that influence the Value of H latt : forces of attractions between Unlike charges
( +ve & -ve )
1. Sum of ionic Radii of ions / or distance between ions The force is given by Coulomb's law :
F = K Q1  Q2 / r2

H lattice becomes less exothermic as the sum of ionic radii or distance (size) between the
ions increases.

[ If sum of ionic radii increases, there will be weaker electrostatic attraction between the
oppositely charged ions]

2. Charges on ions
L.E becomes more exothermic as the magnitude of the charge of the ions increases.
Reason: There will be stronger electrostatic attraction between the oppositely charged ions.

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 15


Theoretical values of L.E can be calculated assuming that the solid or substance is
100% ionic.
/ or ions are as point charges. It can be found experimentally from Born-Haber cycles

 The experimental (from Born Haber) and theoretical values of the L.E are almost
the same for a purely ionic model. [Good fit]

Hlatt(Exp.)  Hlatt(Theor.)  purely ionic

 The experimental values of L.E (from Born Haber) are bigger (more exothermic)
than the values calculated from a purely ionic model only if the bonding has a
significant degree of covalent character in an ionic bon , due to the polarisation of
the anions by the cations.

Hlatt(Exp.) is more Exothermic than Hlatt(Theor.)


The polarisation of anions by cations leads to some covalency in an ionic bond.

Teacher's Tips "How to avoid common mistakes in Exams"

Na2O
2 moles of Na+ 1 mole of O2
so 2  I.E1 so 1  ( E.A1 + E.A2 )

2 Na+ O2
+1 means I.E1 - 2 means E.A1 + E.A2

CaCl2
2 mole of Cl
1mole of Ca2+ so 2   Ha(Cl)
so 1   Ha Ca 2  E.A1
1  ( I.E1 + I.E2 )
Ca2+ 2Cl
charge = +2  I.E1 + I.E2 - 1 means E.A1
Ca2+ forms we include the 1st and 2nd ionisation energies of magnesium
( and not 2 1st ionisation energy !
Since 2 chloride ions 2Clare involved , so we double all quantities i.e 2  Ha ; 2  E.A1
(not 1st + 2nd E.A)

AL –Chemistry 2020-2021 [ Topic_ Lattice Enthalpy] AOUDI 16

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