Calorimetry:

Determination of Heats of Solution

CHEM 1001/1005 (pages: 46-55)

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 Goals
• Measure the heat capacity (Ccal) of a constant-
pressure calorimeter

• Determine the heat of solution (ΔHsol’n) of

 (anhydrous) Sodium acetate (Na2C2H3O2)
 Sodium acetate trihydrate (Na2C2H3O2•3H2O)

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 Theory: First Law of Thermodynamics
• Heat (q) of the universe is ZERO
quniverse = 0
qwarm + qcool + qcalorimeter = 0
qreaction + qsolution + qcalorimeter = 0

So, qcalorimeter = - (qwarm + qcool )

and qreaction = - ( qsolution + qcalorimeter ) = ΔHreaction
because ΔP = 0

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 Theory: Heat Capacity vs. Specific heat
• Heat capacity (C)
qcalorimeter = - (qwarm + qcool ) = Ccalorimeter  T

• Specific heat ()

q = m  water  T
= m  4.184 J/(g* C)  T
(q: qwarm, qcool, qsolution)

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 Apparatus

Note: When shaking the calorimeter,

DO NOT allow the GoLink device
to move around. It may get damaged!
Hold the calorimeter
by the tubing when
stoppering/removing
temperature probe.

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 Procedure: I. Measure heat of solution
• Dry calorimeter and thermometer
• Collect water (35.0 mL), add to calorimeter, record Ti
• Weigh (use weighing bottle) NaC2H3O2 (1.50 g). Do this
quickly on a top-loading balance!!
• Transfer NaC2H3O2 to calorimeter, record Tf
• Repeat with 2.00 g, 2.50 g, 3.00 g of NaC2H3O2
Trial Mass Ti (˚C) Tf (˚C)
(g)
 Repeat for NaC2H3O23H2O 1 1.50
(have one table for each salt) 2 2.00
3 2.50
4 3.00

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 Procedure: II. Calibrate the calorimeter (3 trials)
• Set up the calorimeter (get warm water heating to save time!)
• Collect water (15.0 mL) to calorimeter, record T1i
• Warm up water to 80oC, collect 20.0 mL into a
styrofoam cup, to record T2i Logger Pro Measurements
“Collect” (at the start of trial)
• Pour them to calorimeter, record Tf Shake 60s
Wait 100s
Record temperature
Note: Equations on P.52 for calculation of CCalorimeter
Volume (mL) Mass (g) T (˚C)
Cool (room temperature water) 15.0 15.0 T1i Logger Pro

Warm (heated water) 20.0 20.0 T2i Regular thermometer

Calorimeter (mixed water) Tf Logger Pro

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Pop Question: What’s wrong with this picture?

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 Things to Remember…
• NaC2H3O2 is hygroscopic, weigh & transfer it fast
• Record exact mass (analytical balance) and volume (graduated
cylinder)
• Volume must be exactly what is prescribed
• Dry calorimeter & thermometer before each run
• Distilled water should be room temperature. Can use bottle.
• Uncertainty of top-loading balance ( 0.01 g), 50ml-graduated
cylinder ( 0.1 mL), thermometer ( 0.1oC and 0.2oC)
• Molar heat of solution of sodium acetate (-17.3 KJ/mol) and
sodium acetate trihydrate (19.7 KJ/mol) at 25oC
• Clean up and inventory your station before you’re signed out.
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After-lab Write-up DUE: Next lab Period
Calculation
1. Heat capacity of your calorimeter
2. Molar heat of solution of sodium acetate and sodium acetate trihydrate for each
experiment you carried out. Tabulate the values. (Eight values in total)
3. Average value for each molar heat of solution, and compare them with the accepted
values. Calculate the relative spread and relative error
Discussion
- Around one paragraph, discussion high/low results and questions 4 and 5 on lab manual
See P.55
Conclusion
- One or two sentences, summary of all results

Quality of discussion and conclusion (what we look for in these sections)

1. In discussion – list two reasons why results are high/low and answers of questions
4&5
2. In conclusion – report the heat capacity of your calorimeter, average ΔH values,
relative errors, relative spreads

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2. Molar Heat of solution, ΔHm
ΔHm= - [ qsolution + qcalorimeter ]/moles of Na2C2H3O2

= - [ (msolution*ρsolution* ΔTsolution) + (Ccal * ΔTcal) ]

moles Na2C2H3O2
Note: msolution = msalt + mwater
ρsolution = 4.184 J/(g*°C)
ΔT = Tfinal - Tinitial

3-iii. Relative Error: | Accepted value - Experimental value | X 100%

(a.k.a. % Error) Accepted value

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 • Anhydrous NaC2H3O2 & NaC2H3O2 ·3H2O

Mass of Volume of Tcool Tfinal T = Tf-Tc Mole Conc. Hm

salt cool water (± 0.1 oC) (± 0.1 oC) (± 0.2 oC) of salt = mole/volume = H/mole
(± 0.01g) (± 0.1mL) (mol) (mol/L) (J/mol)

 1.50 35.0
 2.00 35.0
 2.50 35.0
 3.00 35.0
Note:
1.Mw of anhydrous NaC2H3O2: 82 g/mol
2.Mw of NaC2H3O2 ·3H2O: 136 g/mol
3.H = -[(35.0+mass of salt)×4.184×T+ Ccal×T]

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 • Calorimeter Calibration

Volume of Tcool Volume Thot Tfinal T1 = Tf-Tc T2 = Tf-Th C cal
(± 0.1 oC) oC) oC) oC) oC)
cool water of hot (± 0.2 (± 0.1 (± 0.2 (± 0.3 (J/oC)
(± 0.1mL) water
(± 0.1mL)

15.0 20.0
15.0 20.0
15.0 20.0

Note:
1.C cal = -[15.0×4.184×T1+ 20.0×4.184×T2] ÷ T1

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• Question 5 on the lab manual p55

Anhydrous NaC2H3O3
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molar heat of solution (KJ/mol)

21.5
21
20.5
20
19.5
19
18.5
18
17.5
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0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7
molarity (mol/L)

Na+ -OCOCH3 + H+-OH  Na+-OH + H+-OCOCH3

Note: higher molarity, more H+-OH to be broken, need absorb more
heat, so, higher molar heat of solution.

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 How to calculate Ccal

Ccal = - [(masscold H2O)(ρwater)(Δtcal/coldH2O) + (masswarm H2O)(ρwater)(ΔtwarmH2O)] / Δtcal/coldH2O

SAME

SAME
Heat of solution (ΔH soln) = - [(mass solution)(ρwater)(Δtsoln) + (Ccal)(Δtcal)

Mass of H2O AND salt

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