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Chem 156.1 Experiment 8 (Lattice, Solution, Hydration)

Chem 156.1 Experiment 8 (Lattice, Solution, Hydration)

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Experiment 8: Lattice Enthalpy, Enthalpy of Solution and Enthalpy of Hydration Alma L. Pabilane and Lycelle S. EspaňolChemistry 156.1 FEJ Group 8Mr. Yevgeny Aster Dulla
I.Abstract
Solution formation of an ionic compound in water involves two processes: the first, where the ioniccompound is converted to its gaseous ions, involves lattice enthalpy (ΔH
lattice
); the second, where water moleculescluster around free ions, involves enthalpy of hydration (ΔH
hydration
). Conforming to Hess’ Law, enthalpy of solution isgiven by: ΔH
soln
= ΔH
lattice
+ ΔH
hydration
. Using calorimetry, ΔH
soln
of the ionic salts CaCl
2
, NaCl, KCl, KBr and KIdissolved in water are determined. The calculated ΔH
soln
for 1 g of salt dissolved in 20 mL water are -35.8, 1.76,20.71, 122.43 and 24.77 kJ/mol, respectively. Experimental ΔH
soln
for NaCl, KCl and KI are considerably near thetheoretical values: 3.88, 17.2 and 20.5 kJ/mol, respectively. While that of CaCl
2
’s and KBr’s experimental ΔH
soln
arenot near the theoretical value (-82.9 and 20.0 kJ/mol), they showed the expected sign of ΔH
soln
(endothermicity or exothermicity). The deviation may be due to experimental errors: ineffectiveness of improvised calorimeter, humanerror etc. Partial molar heat of solution (PMHS) of a reactant (salt or water) is given by the slope of the curve whennumber of moles of 
that reactant 
is plotted against the ΔH
soln
with respect to the number of moles of 
that reactant 
.The PMHS of the 5 salts (KI, KCl, KBr, CaCl
2
, NaCl) are -612.3, -112.7, -1540.88, -382.10, and -90.82 kJ/mol,respectively while the PMHS of water determined for each salt are -0.054, -112.72, -321.93, -355.44, and -5.120kJ/mol, respectively. The partial molar heat of solution signifies the amount of energy needed to break the solute-solute or solvent-solvent interactions for solution formation to proceed. ΔH
lattice
is estimated using Kapustinskiiequation and Born-Haber Cycle. Kapustinskii yielded more precise value for ΔH
lattice
. It was observed that ΔH
lattice
decreases with increasing atomic radius for both anion and cation. The ΔH
hydration
was calculated by subtracting the ΔH
lattice
from ΔH
soln
.
II.
Keywords
: Born-Haber cycle, Calorimetry, Enthalpy of solution, Enthalpy of Hydration, Kapustinskii Equation,Lattice enthalpy
III.Introduction
Dissolving a solute to form a solution involvesthe solvation of the solute in a particular solvent atspecified conditions and is affected by the strength of the solute-solute, solvent-solvent, and solute-solventinteractions. This process requires the release(exothermic) or absorption (endothermic) of energy inthe form of heat, and consequently, the characteristicsolubility of ionic substances in water can be describedby the enthalpy changes in a solution, namely; thelattice enthalpy, enthalpy of hydration and enthalpy of solution.The enthalpy of hydration (∆H
hydration
) is theenthalpy change for the production of an ionic solutionfrom one mole of gaseous ions. Directly dependent onthe charge and inversely dependent on the atomic radiiof the ions, enthalpy of hydration values are negativeand are indicative of ion-water interaction. Whensolvents other than water are used, this enthalpychange is called the enthalpy of solvation.The lattice enthalpy (
 ∆
H
LE
or 
 ∆
H
Lattice
) is theenthalpy change for the formation of one mole solidfrom gaseous ions and is also the energy needed tobreak the crystal lattice of an ionic solid. Like theenthalpy of hydration, it is directly dependent on theionic charge but inversely dependent on ionic radius.Two methods can be used to determine the latticeenthalpy: the Born-Haber cycle, which usesmeasurable thermochemical data, and the Kapustinskiiequation, which gives an approximation of the latticeenthalpy given the ionic charges and radii. TheKapustinskii equation for lattice enthalpy is given by,
 ∆
H
lattice
=where,k = 1.2025x10
-4
Jm/mold = 3.45x10
-11
mv = number of ions in the empirical formula of the substancez
(+/-)
= ionic charge of the cation/anion
(+/-)
= ionic radius of the cation/anionThe enthalpy of solution (∆H
soln
) is the enthalpychange for the formation of one mole of solution fromone mole of a solute dissolved and can be calculatedfrom the difference between the enthalpy of hydrationof the ions and the lattice enthalpy. Generally, anegative enthalpy value indicates that the solute issoluble in a given solvent while a large positive valueindicates otherwise.
Chem 156.1 Lattice Enthalpy, Enthalpy of Solution and Enthalpy of Hydration Page 1of 8
 
In the experiment, the goal was to determinethe enthalpy of solution of different solutes (CaCl
2
,NaCl, KCl, KI, and KBr) using the calorimetric methodand to determine the differential heats of solution of solute and solvent.
IV.Experimental
The calorimeter constant of an improvisedStyrofoam calorimeter was initially determined. Using asyringe, 20 mL of distilled water was transferred intothe calorimeter and incubated for 15 mins. to allowequilibration of heat. The equilibrium temperature wasof water in the calorimeter was recorded. In a watchglass, 1.0 ± 0.01 g of calcium chloride (CaCl
2
) crystalswas weighed. Immediately, the CaCl
2
crystals wereadded into the calorimeter. The temperature was readand recorded every five seconds while swirling themixture in the calorimeter continuously until 10temperature readings were obtained. The procedurewas repeated with varying mass of CaCl
2
– 1.5, 2.0, 2.5and 3.0 g with constant volume of water – 20 mL; andvarying volume of water – 18.0, 16.0, 14.0, 12.0 mLwith constant mass of CaCl
2
 – 1.0 g. The procedurewas repeated for other ionic salts in place of CaCl
2
:sodium chloride (NaCl), potassium chloride (KCl),potassium bromide (KBr) and potassium iodide (KI).The heat of solution of each salt wascalculated using the following equations: ΔH
soln
= Q
soln
+ Q
water 
Q
cal
+ Q
soln
+ Q
water 
= 0To calculate partial molar heat of solution of the salt, the number of moles of the salt
(from Part 1,where mass of salt is varying and volume of water isconstant)
is plotted against the calculated ΔH
soln
. For partial molar heat of solution of water, the number of moles of water 
(from Part 2, where volume of water isvarying and mass of salt constant)
was plotted againstthe corresponding ΔH
soln
.
V.Results
Computing for the C
cal
of the calorimeter used:C
cal
= [(10mL)(0.9997g/mL)(20-10
o
C)(4.184J/g
o
C) +(10mL)(0.9956g/mL)(20-30
o
C)(4.184J/g
o
C)]/(20-30
o
C)=0.1696 J/
o
C A.Determination of Partial Molar Heats of Solution A.1 Partial molar heat of solution of KI
Table 1.
Constant water versus varying KI
W
KI
(g)1.011.52.02.53.0V
H2O
(mL)
2020202020
n
KI
6.08x10
-3
9.04x10
-3
0.0120.0150.0181
n
H2O
1.111.111.111.111.11
T
i
(
o
C)
3029.32827.827
T
eq
(
o
C)
28.227.225.524.223.7
Q
soln
(J)
150.63175.61209.21301.26276.15
∆H
soln
(kJ/mol)
24.77419.42617.43420.08415.257
Partial molar ΔH
soln
of KI(kJ/mol)-612.3
Computationsn
H2O
= 20mL(0.998g/mL)(1mol/18.01g)= 1.11 mol H
2
OTrial 1:Q
cal
= C
cal
∆T= (0.1696J/
o
C)(28.2-30
o
C)= -0.305 JQ
H2O
= m
H20
(4.184 J/g
o
C)(∆T)= (20mL)(0.998g/mL)(4.184 J/g
o
C)(28.2-30
o
C)= -150.323 JQ
soln
= -( Q
cal
+ Q
H2O
)= -(-0.305J -150.323J)= 150.628 Jn
KI
= 1.01g KI(1mol/166.00277g)= 6.084x10
-3
mol KI∆H
solution
= Q
soln
/n
salt
=[150.628J(1kJ/1000J)]6.08x10
-3
mol= 24.774 kJ/molTrial 2:Q
cal
= C
cal
∆T= (0.1696J/
o
C)(27.2-29.3
o
C)= -0.237 JQ
H2O
= m
H20
(4.184 J/g
o
C)(∆T)= (20mL)(0.998g/mL)(4.184 J/g
o
C)(27.2-29.3
o
C)= -175.377 JQ
soln
= -( Q
cal
+ Q
H2O
)= -(-0.237J – 175.377J)
Chem 156.1 Lattice Enthalpy, Enthalpy of Solution and Enthalpy of Hydration Page 2of 8
 
= 175.614 Jn
KI
= 1.50g KI(1mol/166.00277g)= 9.04x10
-3
mol KI∆H
solution
= Q
soln
/n
salt
=[175.614J(1kJ/1000J)]9.04x10
-3
mol= 19.426 kJ/molTrial 3:Q
cal
= C
cal
∆T= (0.1696J/
o
C)(25.5-28
o
C)= - 0.424 JQ
H2O
= m
H20
(4.184 J/g
o
C)(∆T)= (20mL)(0.998g/mL)(4.184 J/g
o
C)(25.5-28
o
C)= -208.782 JQ
soln
= -( Q
cal
+ Q
H2O
)= -(-0.424J – 208.782J)= 209.206 Jn
KI
= 2.0g KI(1mol/166.00277g)= 0.012 mol KI∆H
solution
= Q
soln
/n
salt
=[209.206J(1kJ/1000J)]0.0120mol= 17.434 kJ/molTrial 4:Q
cal
= C
cal
∆T= (0.1696J/
o
C)(24.2-27.8
o
C)= -0.611 JQ
H2O
= m
H20
(4.184 J/g
o
C)(∆T)= (20mL)(0.998g/mL)(4.184 J/g
o
C)(24.2-27.8
o
C)= -300.646JQ
soln
= -( Q
cal
+ Q
H2O
)= -(-0.611J-300.646J)= 301.257 Jn
KI
= 2.50g KI(1mol/166.00277g)= 0.0150 mol KI∆H
solution
= Q
soln
/n
salt
=[301.257J(1kJ/1000J)]0.0150mol= 20.084 kJ/molTrial 5:Q
cal
= C
cal
∆T= (0.1696J/
o
C)(23.7-27
o
C)= -0.560 JQ
H2O
= m
H20
(4.184 J/g
o
C)(∆T)= (20mL)(0.998g/mL)(4.184 J/g
o
C)(23.7-27
o
C)= -275.592 JQ
soln
= -( Q
cal
+ Q
H2O
)= -(-0.560J-275.592J)= 276.152 Jn
KI
= 3.00g KI(1mol/166.00277g)= 0.0181 mol KI∆H
solution
= Q
soln
/n
salt
=[276.152J(1kJ/1000J)]0.0181mol= 15.257 kJ/molUsing linear regression, plot ∆H
solution
vs n
solute
.∆H
solution
= n
KI
∆H
solution,KI
+ n
H2O
∆H
solution,H2O
y = mx + by = (-612.3)x + 0.161m = partial molar heat of solution of KI= -612.3 kJ/mol
Figure 1.
Graph for the determination of Partial Molar Heat of Solution of KI with the equation of the best fit line (inset)
The same procedure was done for theremaining salts, and the values are shown in thefollowing tables.
Table 2.
Constant water versus varying KCl
W
KCl
(g)
1.01.52.02.53.0
 
V
H2O
(mL)
2020202020
n
KCl
1.34x10
-2
0.02010.02680.03350.0402
n
H2O
1.1061.111.111.111.11
T
i
(
o
C)
30.726.9262626.5
T
eq
 
(
o
C)
28.123.521.520.920.0
Q
soln
(J)
277.48379.79502.67569.69726.07
∆H
soln
(kJ/mol)
20.7118.8818.7416.9918.04
Partial molar heat of solutionof KCl (kJ/mol)
-112.72
Table 3.
Constant water versus varying KBr 
W
KBr 
(g)
1.011.52.02.53.0
V
H2O
(mL)
2020202020
n
Br 
8.43x10
-3
0.01260.01680.0210.0252
n
H2O
1.111.111.111.111.11
T
i
(
o
C)
32
T
eq
 
(
o
C)
30
Q
soln
(J)
1032
Chem 156.1 Lattice Enthalpy, Enthalpy of Solution and Enthalpy of Hydration Page 3of 8

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