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Born Haber Cycle

Lattice Enthalpy (H latt ) : The enthalpy of formation of 1 mole of a compound from its gaseous ions under standard conditions ((298K, 1atm )

All H latt are exothermic

Gaseous atoms Na + (g) +


Ionization Energy

Cl (g)
Electron Affinity

Na(g) +
Atomization Energy

Cl(g)

Lattice Enthalpy

Gaseous atoms

Elements Na( s ) +
o H lat = H o f

Enthalpy of formation

1 Cl 2( g ) 2

Solid Compound NaCl(s)

( H

o at

+ H io + H e

))

Hf = H1 + H2 + H3+ H4 + H6

For diatomic molecules ( F2 , Cl 2 , Br2 , I 2 , O 2 , H 2 and N 2 )


H atomizatio n =
1 2 1 2

Bond Energy

Cl 2 ( g ) Cl ( g )

H atomizatio n [ 1 Cl 2 ( g )] = 1 E(C l - C l ) 2 2 H atomizatio n [ 1 O 2 ( g )] = 1 E(O - O) 2 2

1 2

O 2(g ) O(g)
Na ( g )

Na ( s )

H atomizatio n

The Born - Haber cycle

Ca 2+ (g) + 2Cl (g) CaCl 2 (s)

H latt [CaCl 2 ( s )] < 0,

Ca 2+ (g) + 2Cl (g)


IE2

Ca 2+ (g) + 2Cl (g)


2 EA1

Ca + ( g ) Ca 2+ (g) + 2Cl - (g)


IE1

2H at [ 1 Cl 2 ( g )] = 2

E (Cl Cl )

Ca(g)

H at [Ca( s)] H latt


Elements Ca ( s) + Cl 2 ( g )

H f
CaCl2 (s)

Factors that affect the lattice energy are:


Sizes (radii) of the ions Charges on the ions

The smaller the ions and the higher the charges on these ions, the more negative the lattice enthalpy The larger the ions and the smaller the charges on these ions, the less negative the lattice enthalpy

Explanation: - In smaller ions the outer electrons are closer to the positive nucleus; hence the attractive force of nucleus holds them more tightly. lattice energy becomes more negative (larger)

MgF2
CaF2
-

r ( Mg 2+ ) = 0.072nm

H lat =
-2957 kJ .mol 1 H lat =

H lat [ MgF2 ( s )] > H lat [CaF2 ( s)]

r (Ca 2+ ) = 0.10nm

Because r ( Mg 2+ ) < r (Ca 2+ )

-2630 kJ .mol 1

the higher the charges on one or both of the opposite ions the stronger the attractive force between them
lattice energy becomes more negative (larger)
2

The table shows how increasing the charge on either of the ions increases the lattice enthalpy

Charge on CATION is increasing NaCl MgCl2 AlCl 3

H lat / kJ .mol 1 is increasing -771 -2493 - 4500

Charge on ANION is increasing MgCl 2 MgO

H lat / kJ .mol 1 is increasing -2493 -3889

Exercise: Which of the following has the largest lattice enthalpy? a) NaF, CaF2 or AlF3 b) NaCl, CaCl 2 or Al 2 O3 c) CaF2 , MgF2 Answer a)
AlF3 ( Al 3+ ion is smaller and has higher charge than Na + and Ca 2+ )

the attractive force between their opposite charges is stronger and the nucleus of Al 3+ holds the electrons on F more tightly.
Al 2 O3 ( Al 3+ and O 2 ions are smaller and has higher charges) MgF2 ( F ion is the same in both compounds, but Mg 2+ ion is smaller than Ca 2+ )

b) c)

Polarizing power of small cations having high charge and polarizability of large anions and their effect on the nature of the bond
Polarization is due to - Size and charge of the cation - Only size of the anion Small cation, with large positive charge have high polarizing power The larger the anion, the more easily it is polarized Small cations with high positive charge polarize large anions more and DISTORT the ionic bond and result in a considerable degree of covalent character

Theoretical H lat ( AgCl ) is less negative than the Experimental H lat ( AgCl )
silver ion is small ( has high polarizing power), it polarized chloride ion and caused distortion of the ionic bond. This results in a considerable degree of covalent character (sharing electrons)

+
pole

pole

polarizati on

Nopolariza tion

Predicting how ionic a bond is from LATTICE enthalpy DIFFERENCE


Enthalpy DIFFERENCE: The difference between the EXPERIMENTAL value (calculated by Born Haber Cycle) and the THEORETICAL value (determined using the ionic sizes and charges)

When the enthalpy difference is small (less than 5 %), the bond is almost pure ionic When the enthalpy difference is big (more than 5 %), the bond has a considerable degree of covalency , that is sharing of electrons

Therefore the difference is due to the covalent character which is not considered in theoretical calculation

Predicting stability of a compound over others from H o calculated from f Born Haber Cycle
The more negative the H o of a compound the more stable it is and the more likely to be formed f The more positive H o of a compound the less likely to be formed as it requires energy to be f formed. Therefore, less stable it is

From Comparison between THERRETICAL and EXPERIMENTAL lattices , to degree of covalency , stability and solubility

2Al3+ (g) + 3O(g)


2H i3 [ Al 2+ ( g )]

2Al3+ (g) + 3O(g)


3H e1 [O( g )]

2Al3+ (g) + 3O - (g)


2Al 2+ ( g ) 2H i2 [ Al ( g )] 2Al ( g ) 2H i1 [ Al ( g )] 2Al (g) 2H at [ Al ( s)]
Elements 2 Al ( s ) + 3 O2 ( g ) 2
+

3H e2 [O - ( g )] 3H at [ 1 O 2 ( g )] = 2
3 2

E (O O )

2Al3+ (g) + 3O 2- (g)

H latt

H f
Al 2 O 3 (s)
o H lat = H o f

( H

o at

+ H io + H e

))

The lattice Enthalpy is very highly exothermic the first electron affinity of the very electronegative elements such as nitrogen, oxygen and halogens are endothermic

Question 1: Paper 4 Jun 2008 / Q 4


(a) The following data were collected in a Born Haber cycle for silver fluoride, AgF.
value / kJ .mol 1 +285

Enthalpy of atomization of silver First ionization energy of silver enthalpy of atomization of fluorine Enthalpy of formation of silver fluoride Lattice energy of silver fluoride

+731 +79 -205 -958

(i) On the following outline of Born Haber cycle, complete the boxes A and B by adding the formula and state symbol for the appropriate species. Write the name of enthalpy change C.

Ag + ( g )

F (g)

AgF(s)

Box A

Box B

C .....................................

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

Ag(s) +

1 2

F2 (g)
[3]

(ii) Use the data to calculate the first electron affinity of fluorine.

[2]

(b) H latt (Theoretical) is the lattice energy calculated assuming the crystal lattice is completely ionic.
H latt (Experimental) is the lattice energy determined experimentally using the Born Haber cycle The values for silver halides are listed below.

Formula of halide
AgF AgCl AgBr AgI

H latt (Theoretical) / kJ .mol 1 -920 -833 -816 -778

H latt (Experimental) / kJ .mol 1 -958 -905 -891 -889

H latt (Theoretical) minus H latt (Experimental) / kJ .mol 1 38 72 75 111

(i) Explain why the theoretical lattice energies become less exothermic from AgF to AgI.
- anion (X-) size increases down group (1) - Charges (on anions) are the same (1) - so forces of attraction between ions become weaker(from AgF to AgI) (1)

[3]

(ii) Explain why the values of the theoretical and experimental lattice energies are different.

Theoretical value assumes 100% ionic, no covalent character (1)

- (Experimental value is different) due to covalent character OR polarisation

of anion by the cations / distortion of the anion(1)


[2]

(iii)Explain why the difference between the theoretical and experimental lattice energies increases from AgF to AgI.

(as) size of anion increases down group (1) of anion (1)

- so anions become more easily polarised (down) group OR more distortion

[2]

Question 2: Paper 4 Jan 2008 / Q 3


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

Ca 2+ (g) +

2e

+ 2H(g)

H 4
Ca 2+ (g) + 2e + H 2 (g) Ca 2+ (g)

H 5
+ 2H (g)

H 3
Ca(g) + H 2 (g)

H 2
Ca(s) + H 2 (g)

H 6

H1
CaH 2 (s)

(a) Write down in terms of one of the symbols H1 to H 6 . (i) The lattice energy of calcium hydride .. (ii) *The first electron affinity of hydrogen.
[1] [1]

(b) Use the data in the table below to calculate the enthalpy of formation of calcium hydride, CaH2(s) value / kJ .mol 1 Enthalpy of atomization of calcium +178
First plus second ionization energies of calcium enthalpy of atomization of hydrogen First electron affinity of hydrogen Lattice energy of calcium hydride +1735 +218 -73 -2389

Calculation:

[2]

(c) Explain why the lattice energy of magnesium hydride, MgH2(s), is more exothermic than the lattice energy of calcium hydride, CaH2(s).
- Mg2+ ion is smaller than Ca2+ ion (1) - but charges are the same (1) - so stronger (forces of) attraction between ions in MgH2(s) (1)

[3]
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Question 3: Paper 4 Jan 2009 / Q 2


(a) Define the term lattice energy.

[2]

(b) Use the energy cycle and the data to calculate the lattice energy of barium chloride.

Ba 2+ (g) + 2Cl (g) + 2e

Ba 2+ (g)

+ 2Cl (g)

Ba(g) + 2Cl (g)

Ba(g) + Cl2 (g)

Ba(s) + Cl2 (g)

BaCl (s)

Enthalpy of formation of BaCl2(s) enthalpy of atomization of barium enthalpy of atomization of chlorine 1 +2


st nd

value /kJ.mol-1 -859

+180 +122 +1468 -349

ionization energies of barium

First electron affinity of chlorine Calculation:

[3]

(c)(i) Explain how comparison of lattice energies from the Bor Haber cycle with theoretical lattice energies provodes evidence for the nature of the bonding in the chlorides of the group 2 metals.

Theoretical model is based on 100% ionic bonding (1)

If experimental Born Haber value is different or more exothermic / bigger this is due to some covalency or some covalent character in the bonding (1)

[2]

(ii) Explain the difference in bonding between beryllium and chlorine and that between barium and chlorine.

- Be ion or beryllium ion is smaller (than the Ba ion (and have the same charge) (1) - Be ion polarizes /distorts the chloride ion more (than Ba does), leading to covalency / covalent character (1)

2+

2+

2+ 2+

[2]

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Question 4: Paper 4 Jan 2007 / Q 5


(a) A Born-Haber cycle for the formation of magnesium chloride is shown below.

Mg(g) + 2Cl (g)

+ 2e

Mg 2+ (g) + Cl2 (g) + 1e

Mg 2+ (g) + 2Cl (g)

Mg + (g) + Cl2 (g) + 1e

Mg(g) + Cl2 (g)

Mg(s) + Cl2 (g)

MgCl2 (s)

enthalpy of atomization of magnesium 1st ionization energy of magnesium 2


nd

value /kJ.mol-1 +150 +736 +1450 +122 -642 -2526

ionization energy of magnesium

enthalpy of atomization of chlorine Enthalpy of formation of magnesium chloride Lattice energy of magnesium chloride

(i) Use the data to calculate the first electron affinity of fluorine.

[2]
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(ii) The theoretically calculated value for the lattice energy of magnesium chloride is 2326 kJ.mol1
Explain, in terms of the bonding in magnesium chloride, why the experimentally determined value of 2526 kJ.mol1 is significantly different from the theoretical value.

2+

MgCl2 has (a degree of ) covalent character (1) due to polarisation of the anion by the small Mg

cation (1)

[2]

(b) The table shows values for the lattice energies of the metal chlorides of some Group 2 metals. Group 2 metal chloride Lattice energy/ kJ.mol-1
MgCl2 -2526 CaCl2 -2237 SrCl2 -2112 BaCl2 -2018

Explain why these lattice energies become less exothermic from MgCl2 to BaCl2.

- radius of M 2+ (ion) increases down the group (1) - Charge on ions remains the same/2+ (1) - so down the group forces of attraction between ions become weaker (1)

[2]

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