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Lattice Hydration Solution

This document summarizes an experiment to determine the enthalpies of hydration for various ions. Salt samples were dissolved in a calorimeter and the temperature change was used to calculate the molar enthalpy of solution. These values, along with literature data, were used to calculate the enthalpies of hydration for each ion. The calculated values matched literature values within 7% on average, though the uncertainties were likely underestimated. Enthalpies of hydration tended to increase with greater ion charge. Repeating the experiment with more precise instruments could provide a better estimate of uncertainty.

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70 views6 pages

Lattice Hydration Solution

This document summarizes an experiment to determine the enthalpies of hydration for various ions. Salt samples were dissolved in a calorimeter and the temperature change was used to calculate the molar enthalpy of solution. These values, along with literature data, were used to calculate the enthalpies of hydration for each ion. The calculated values matched literature values within 7% on average, though the uncertainties were likely underestimated. Enthalpies of hydration tended to increase with greater ion charge. Repeating the experiment with more precise instruments could provide a better estimate of uncertainty.

Uploaded by

Erica Bradley
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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hjWesley Viola (Dan Bowen, Jingcheng Huang)

Date performed, due, submitted: 10/19;11/7;11/10


Experiment 7 Calorimetry Enthalpy of Solution/ Enthalpy of
Hydration
Abstract:
In this lab, the enthalpies of solution for five ionic solids were
determined and from these values (along with other information from
literature), enthalpies of hydration for the constituent ions were
determined. This was accomplished by measuring the temperature
change in a calorimeter as each of the salts were dissolved and
determining the heat change by multiplying the temperature change
by the heat capacity of the calorimeter. The molar heats of solution
were then found and with these values, along with lattice enthalpies
and the enthalpy of hydration of chloride, the enthalpies of hydration
of all the constituent ions were determined.
The calculated enthalpies of hydration and the associated
uncertainties can be found in Table 5 as well as the true values. The
experimentally determined values differ by the true values by only
about 7% on average, a fairly good correspondence. The true values
do fall out of the error windows which seem smaller than they should
be.
Introduction:
The dissolving of ionic solids in water involves a breaking of ionic
bonds of the solid and a formation of new, ion-dipole bonds between
the ions and the water molecules. The enthalpy associated with the
breaking of the ionic bonds is called the lattice enthalpy of the ionic
solid and the enthalpy associated with the formation of the ion-dipole
bonds is called the enthalpy of hydration. The enthalpy of the overall
process, the heat of solution, is the sum of these two enthalpies:
H lattice + H hydration =H solution
Thermodynamic cycle:

Depending on the strength of the lattice bonds and the strength


of the ion-dipole bonds, the enthalpy of solution may be positive or

negative. When it is a positive value, heat is absorbed by the


dissolved solid and when it is negative, heat is released.
An excellent way to measure the loss or absorption of heat in
the dissolution is by using a calorimeter. A calorimeter is an insulated
vessel in which one can accurately measure the temperature change
resulting from the dissolution of the ionic solid in water. The enthalpy
change is then simply the temperature change multiplied by the heat
capacity of the water and the container.
Though exothermic (negative H) reactions are often
spontaneous, the H of a reaction does not need to be negative for it
to be spontaneous. As seen in the Gibbs free energy equation (where
a negative G indicates a spontaneous reaction), spontaneity is
determined by contributions from both enthalpy and entropy changes:
G= HT S
A reaction can be endothermic and spontaneous if the TS term
(representing the increase in entropy) is sufficiently large.
Being able to determine the enthalpy of a reaction relatively
simply is very significant since H is related by the Gibbs free energy
equation to the reactions entropy change, a very difficult quantity to
directly measure.
Experimental Methods:
The procedure outlined in the lab handout Experiment 7 - Calorimetry
Enthalpy of Solution/ Enthalpy of Hydration was followed with a few
exceptionsA. Due to mistakes with using not anhydrous salts, the trials
of a few salts the LiNO3, LiNO3, and CaCl2 - had to be rerun to obtain
correct data. Another trial of KNO3 also had to be rerun due to an
insufficient lead out time.

Results:
Table 1. Masses of ionic solids used in dissolutions. The change in
temperature of the water and the heat capacity of the system for each
solid are also included.
Compou
nd

Mass (g) (+/- .


0005 g)

Correcte
d q (cal)

delta T (c) (+/- .


00005 C)

LiNO3

0.0697

0.50577

0.01800

Heat
Capacity
(cal/C) (+/.05 cal/C)
28.1054

LiNO3
LiNO3

0.0691
0.0691

0.54030
0.55972

0.02001
0.01932

27.0040
28.9691

NH4NO3
NH4NO3
NH4NO3

0.1012
0.0809
0.0813

-5.96613
-6.19571
-5.53786

-0.21297
-0.22415
-0.19904

28.0137
27.6408
27.3230

KCl
KCl
KCl

0.0743
0.0744
0.0804

-4.20122
-4.34969
-4.71483

-0.15212
-0.15707
-0.16933

27.6173
27.6923
27.8449

CaCl2
CaCl2

0.1100
0.1111

8.24343
8.07717

0.30282
0.29623

27.2219
27.2661

KNO3
KNO3
KNO3

0.1023
0.1012
0.1012

-8.72328
-8.27855
-8.42838

-0.32053
-0.03036
-0.30683

27.2148
27.2724
27.4692

Discussion:
Table 2. The average masses and heats of solution of different salts.
Compou
nd
LiNO3
NH4NO3
KCl
CaCl2
KNO3

Uncertai
Uncertai
Average nty (+/Average nty (+/Mass (g) g)
q ( J)
kJ)
0.0693
0.0005 2.24007 0.00682
24.6910
0.0878
0.0005
8 0.00478
18.5057
0.0764
0.0005
1 0.00217
0.1106
0.0005 34.1509 0.02068
0.1016
0.0005 35.4751 0.00287

Table 3. The average T and heat capacities of salts.


Compoun
d

Average
T (C)

Uncertainty (+/C)

Average energy
equivalent (J/C)

Uncertai
nty (+/J/C)

LiNO3

0.019108

0.00005

117.23

0.05

NH4NO3

-0.212053

0.00005

116.44

0.05

KCl

-0.159507

0.00005

116.02

0.05

CaCl2

0.299529

0.00005

114.02

0.05

KNO3

-0.219240

0.00005

161.81

0.05

Table 4. Calculated moles of dissolved salts and the heats of solutions.


Compou
nd
LiNO3
NH4NO3
KCl
CaCl2
KNO3

Moles (n)
0.00101
0.00110
0.00102
0.00100
0.00100

Uncertainty
H sol
Uncertainty (+/(+/- n)
(kJ/mol)
kJ/mol)
0.034473
2.23
0.064931027
0.040026
-22.51
0.616409956
0.0372755
-18.07
0.496081421
0.05549
34.28
0.615250042
0.0505515
-35.31
0.701484263

Table 5. Calculated enthalpies of hydration for the constituent ions of


the ionic solids studied in this lab and actual valuesB.
Species
ClCa2+
K+
NO3Li+
NH4+

H hydration
(kJ/mol)
-364
-1497.71631
-369.06579
-353.24747
-492.52390
-345.26472

Uncertainty (+/kJ/mol)
0
0.61525
0.49608
1.19757
1.26334
1.81398

Actual H hydration
(kJ/mol)
-378
-1579
-320
-314
-520
-307

The calculations for this lab began with simple averaging of data
from three different trials to obtain Tables 2 and 3. The heat change
was obtained by multiplying the change in temperature of the system
by its heat capacity the uncertainty for the calculated values was
obtained using the range method of error propagation (this method
was used for all error analysis)1. The moles of the ionic solids were
found using molar masses from literature. The molar enthalpies of

solution were then calculated2. Finally, the enthalpies of hydration for


each constituent ion could be calculated by using the experimentally
determined heats of solution, the lattice enthalpies of the ionic solids
found in literature, and the enthalpy of hydration of the chloride ion3.
The calculated enthalpies of hydration were fairly close to the
actual values, as seen in Table 5, showing an average discrepancy of
about +/- 42 kJ/mol or 7% error. While the accuracy of the calculated
values is acceptable, the true values do not fall within the error window
given by the uncertainty analysis. Propagating the assumed
uncertainty values for the T and heat capacity measurements yielded
quite small uncertainties in the final calculated values, about .25% of
the values themselves. Since the heats of hydration are fairly close to
the true values, indicating the legitimacy of the experimental methods,
it is likely that the precision of the instruments used was assumed to
be greater than it actually is. The fact that the error in the enthalpies
of hydration is not biased in one particular direction also lends
credibility to the explanation that random, indeterminate error of the
instruments is the major source of error.
For LiNO3 and CaCl2, the enthalpy of solution was found to be
positive, meaning heat was absorbed by the salt as it dissolved.
Despite being endothermic, these processes happened spontaneously.
If H is positive as it is in these reactions, the contribution of entropy
change to the Gibbs free energy (TS) must be of greater magnitude
than that of H for G to be negative.
The calculated enthalpies of hydration can be analyzed based on
the size and charge of the ion. It appears that the enthalpy of
hydration tends to increase with increasing charge (Ca2+ for example
is the largest and most positively charged ion studied and shows the
highest enthalpy of hydration). This could be explained physically in
that a stronger bond can be formed between two species when they
have charges of greater magnitude. There is not as clear of a trend for
ionic size relative to enthalpy of hydration. While Cl- is likely the
smallest ion of the five, its enthalpy of hydration does not differ
significantly from the others and a trend is not clearly seen.
Overall, the experiment seems to be a success since the
calculated enthalpies of hydration differ from the true values by only
about 7%. If this lab were to be repeated, it would be a good choice to
determine the imprecision of the instruments used to prove that the
error of the calculations is due to just random error.

References:
A. Course Document Experiment 7 Calorimetry Enthalpy of
Solution/ Enthalpy of Hydration, Course Website on Trunk
B.
http://intro.chem.okstate.edu/1515sp01/lecture/chapter13/lec21601.ht
ml

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