SCIENCE OF CALORIMETRY

Heat (q)
• Heat: the transfer of energy between objects due to a
temperature difference
• Flows from higher-temperature object to lower-temperature
object

If T1 > T2
System Heat Surroundings
(T1) (T2) q system = -
exothermic

If T1 < T2
System Heat Surroundings
(T1) (T2) q system = +
endothermic
 Calorimetry: the measurement of heat flow
• device used is called a... calorimeter
specific heat capacity (C): amt. of heat needed to raise
temp. of 1 g of a substance 1oC (1 K)

• Only useable within a state of matter (i.e. s, l, or g)

For energy changes involving…

heat of fusion (ΔHfus): melting/freezing
heat of vaporization (ΔHvap): boiling/condensing
There are NO temp changes during a phase change.
Various Specific Heat Capacities
Specific
Substance heat capacity
(J/K g)

Gold 0.129 Metals do not

generally
Silver 0.235
require much
Copper 0.385 energy to heat
Iron 0.449 them up
(i.e. they heat
Aluminum 0.897
up easily)
H2O(l) 4.184 Water requires
H2O(s) 2.03 much more
energy to heat
1.998
H2O(g) up
We can find the heat a substance loses or gains using:
where q = heat (J) q = m C DT
m = mass of substance (g)
(used within a given
C = specific heat (J/goC) state of matter)
DT = temperature change (oC)
AND
DH = heat of vap/fus (J/g)
q = m ΔH
Heating Curve
g (used between two
+ l/g Cg
Temp.

ΔHvap
states of matter or
l
s/l Cl during a phase change)
s ΔHfus –
Cs
D = final – initial
HEAT
Using heat capacities…

q = m  C  ΔT
q (J) = mass (g)  C (J/goC)  ΔT (oC)
q = joules (J)

Mnemonic device: q = m “CAT”

 Heating Curves
• Temperature Change within phase
• change in KE (molecular motion)
• depends on heat capacity of phase
C H2O (l) = 4.184 J/goC (requires the most heat)
C H2O (s) = 2.077 J/goC
C H2O (g) = 2.042 J/goC (requires the least heat)
• Phase Changes (s ↔ l ↔ g)
• change in PE (molecular arrangement)
• temperature remains constant
• overcoming intermolecular forces
ΔHfus = 333 J/g (s ↔ l)
ΔHvap = 2256 J/g (l ↔ g) Why is this so much larger?
 Heating Curve of Water
From Ice to Steam in Five Easy Steps

q4 q5

q1: Heat the ice to 0°C

q1 = m Cs ΔT
q3 q2: Melt the ice into a liquid at 0°C
q2 q2 = m ΔHfus
q3: Heat the water from 0°C to 100°C
q3 = m Cl ΔT
q1 q4: Boil the liquid into a gas at 100°C
Heat q4 = m ΔHvap
Heat
q5: Heat the gas above 100°C
q5 = m Cg ΔT
qtot= q1 + q2 + q3 + q4 + q5
 Heating Curve Practice
1. How much energy (J) is required to heat
12.5 g of ice at –10.0 oC to water at 0.0 oC?
4 5 Notice that your q values are
positive because heat is added…
3
2
q1: Heat the ice from -10 to 0°C
1
q1 = 12.5 g (2.077 J/g oC)(0.0 - -10.0 oC) =259.63 J
q2: Melt the ice at 0°C to liquid at 0 oC
q2 = 12.5 g (333 J/g) =4162.5 J

qtot = q1 + q2 = 259.63 J + 4,162.5 J = 4,420 J

 Heating Curve Practice
2. How much energy (J) is required to heat 25.0
g of ice at –25.0 oC to water at 95.0 oC?
Notice that your q values are
4 5 positive because heat is added…

3 q1: Heat the ice from -25 to 0°C

2 q1 = 25.0 g (2.077 J/g oC)(0.0 - -25.0 oC) = 1298.1 J
1
q2: Melt the ice at 0°C to liquid at 0 oC
q2 = 25.0 g (333 J/g) = 8325 J
q3: Heat the water from 0°C to 95 °C
q3 = 25.0 g (4.184 J/g oC)(95.0 – 0.0oC) = 9937 J

qtot = q1 + q2 + q3 = 1298.1 J + 8,325 J + 9937 J = 19,560 J

 Heating Curve Practice
3. How much energy (J) is removed to cool 50.0 g of steam
at 115.0 oC to ice at -5.0 oC?
Notice that your q values are
4 5 negative because heat is removed…
q5: Cool the steam from 115.0 to 100°C
3
2 q5 = 50.0 g (2.042 J/g oC)(100.0 - 115.0 oC) = -1531.5 J
q4: Condense the steam into liquid at 100°C
1 q4 = 50.0 g (- 2256 J/g) = -112,800 J
q3: Cool the water from 100°C to 0 °C
q3 = 50.0 g (4.184 J/g oC)(0.0 – 100.0oC) = -20920 J
q2: Freeze the water into ice at 0 °C
q2 = 50.0 g (- 333 J/g) = -16650 J
q1: Cool the ice from 0°C to – 5.0 °C
q1 = 50.0 g (2.077 J/g oC)(- 5.0 – 0.0oC) = -519.25 J

qtot = q1 + q2 + q3+ q4 + q5 = -1531.5 J + -112,800 J + -20920 J + -16,650 J + -519.25 J =

-152,000 J
 Food and Energy

Caloric Values
Food joules/gram calories/gram “Calories”/gram
Protein 17,000 4,000 4

Fat 38,000 9,000 9

Carbohydrates 17,000 4,000 4

1 calorie = 4.184 joules 1000 calories = 1 “Calorie”

"science" "food"
or… 1 Kcal = 1 “Calorie”
 Does water have negative calories?
How many Calories (nutritional) will you burn by
drinking 1.0 L of water, initially at 36.5 oF (standard
refrigeration temperature)? Assume that the body
must expend energy to heat the water to body
temperature at 98.6 oF. 37 oC
1 L = 1000 mL 2.5 oC
5
C   F  32  1 mL = 1 g
9
1 calorie = 4.184 joules
q  mCT 1000 calories = 1 “Calorie”

q = 1.0 x 103 g (4.184 J/g oC)(37 oC - 2.5 oC) = 144,348 J

144348 J 1 cal 1 “Cal”
= 35 Cal
4.184 J 1000 cal
What will happen over time?

Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 291

Let’s take a closer look…
Eventually, the temperatures will equalize
 Much calorimetry is carried out Thermometer

using a coffee-cup calorimeter,

under constant pressure
(i.e. atmospheric pressure) Styrofoam
cover
• If we assume that no heat is Styrofoam
cups
lost to the surroundings, then the
energy absorbed inside the
calorimeter must be equal to the
Stirrer
energy released inside the
calorimeter.
i.e., q absorbed = – q released

qx = – qy
 1. A 75.0 Heat Transfer
g piece Experiments
of lead (specific heat = 0.130
J/goC),
initially at 435oC, is set into 125.0 g of water, initially
at 23.0oC. What is the final temperature of the
mixture?

Pb
What is the final
75.0 g 125 g temperature, Tf, of
435.0 °C 23.0 °C
C = 0.130 J/°C g the mixture?
qwater = –qPb
q = m x C x ΔT for both cases, although specific values differ
Plug in known information for each side
Solve for Tf ...
 A 75.0 g piece of lead (specific heat = 0.130 J/goC),
initially at 435oC, is set into 125.0 g of water, initially
at 23.0oC. What is the final temperature of the
mixture?
q = m x C x ΔT for both cases, although specific values differ
Plug in known information for each side
qwater = –qPb

mwater Cwater DTwater = –mPb CPb DTPb

125 (4.18) (Tf – 23) = –75 (0.13) (Tf – 435)
522.5 Tf – 12017.5 = –9.75 Tf + 4241.25
+9.75 Tf +12017.5 +9.75 Tf +12017.5
532.25 Tf = 16258.75
Tf = 30.5oC
2. A 97.0 g sample of gold at 785oC is dropped into 323 g of
water, which has an initial temperature of 15.0oC. If gold has a
specific heat of 0.129 J/goC, what is the final temperature of the
mixture? Assume that the gold experiences no change in state
of matter. T = 785oC
Au
mass = 97.0 g

T = 15.0 oC
mass = 323 g

- LOSE heat = GAIN heat

- [(C Au) (mass) (DT)] = (C H2O) (mass) (DT)
- [(0.129 J/goC) (97 g) (Tf - 785oC)] = (4.184 J/goC) (323 g) (Tf - 15oC)]
- [(12.5) (Tf - 785oC)] = (1.35 x 103) (Tf - 15oC)]
-12.5 Tf + 9.82 x 103 = 1.35 x 103 Tf - 2.02 x 104
3 x 104 = 1.36 x 103 Tf
Tf = 22.1oC
HW #2. If 59.0 g of water at 13.0 oC are mixed with 87.0
g of water at 72.0 oC, find the final temperature of the
system.

T = 13.0 oC T = 72.0 oC
mass = 59.0 g mass = 87.0 g

- LOSE heat = GAIN heat

- [ (mass) (C H2O) (DT)] = (mass) (C H2O) (DT)
- [ (59 g) (4.184 J/goC) (Tf - 13oC)] = (87 g) (4.184 J/goC) (Tf - 72oC)]
- [(246.8) (Tf - 13oC)] = (364.0) (Tf - 72oC)]
-246.8 Tf + 3208 = 364 Tf - 26208
29416 = 610.8 Tf
Tf = 48.2oC
 HW #4. 240. g of water (initially at 20.0oC) are mixed with an
unknown mass of iron initially at 500.0oC (CFe = 0.4495 J/goC).
When thermal equilibrium is reached, the mixture has a
temperature of 42.0oC. Find the mass of the iron.
T = 500oC
Fe
mass = ? grams

T = 20oC
mass = 240 g
- LOSE heat = GAIN heat
-q1 = q2
- [ (mass) (CFe ) (DT)] = (mass) (CH2O) (DT)
- [ (X g) (0.4495 J/goC) (42oC - 500oC)] = (240 g) (4.184 J/goC) (42oC - 20oC)]
- [ (X) (0.4495) (-458)] = (240 g) (4.184) (22)
205.9 X = 22091

X = 107 g Fe
 A 23.6 g ice cube at –31.0oC is dropped into 98.2 g
of
water at 84.7oC. Find the equilibrium temperature.
KEY: Assume that the ice melts and the final product is a liquid.
qice = –qwater

qwater = –98.2 (4.18) (Tf – 84.7) = –410.48 Tf + 34767.32

qice = 23.6 (2.077) (0 – –31) + 23.6 (333) + 23.6 (4.18) (Tf – 0)

= 1519.53 + 7858.8 + 98.65 Tf
= 9378.33 + 98.65 Tf
509.13 Tf = 25388.99
Tf = 49.9oC
 Heating Curve Challenge Problems
140 DH = mol x DHvap
1. A sample of ice at -25 C is
o 120
100
DH = mol x DHfus

placed into 75 g of water

80
Heat = mass x Dt x Cp, gas

Temperature (oC)
60
40

initally at 85oC. If the final 20

0
Heat = mass x Dt x Cp, liquid

temperature of the mixture -20

-40
-60

is 15oC, what was the mass -80

-100
Heat = mass x Dt x Cp, solid

of the ice? 52.8 g ice Time

2. A 38 g sample of ice at -5oC is placed into 250 g of water

at 65oC. Find the final temperature of the mixture
assuming that the ice sample completely melts.
45.6 oC

3. A 35 g sample of steam at 116oC are bubbled into 300 g

water at 10oC. Find the final temperature of the system,
assuming that the steam condenses into liquid water.
76.6 oC
 Heating Curve for Water
(Phase Diagram)
F
140 q4 = m DHvap
120 DHvap = +/- 2256 J/g 5
E
100
BP q2 = m DHfus D

DHfus = +/- 333 J/g 4

80 q 5 = m C DT
Temperature (oC)

60 C g = 2.042 J/goC
3
40
q3 = m C DT
20 Cl = 4.184 J/goC
MP B
0 C
2
-20
1 AB warm ice
-40 BC melt ice (s  l)
-60 q1 = m C DT CD warm water
Cs = 2.077 J/goC DE boil water (l  g)
-80 ED condense steam (g  l)
A
EF superheat steam
-100
Heat
Calculating Energy Changes - Heating
Curve for Water

140 DH = mol x DHvap

120 DH = mol x DHfus
100
80
Temperature (oC)

60 Heat = mass x Dt x Cp, gas

40
20 Heat = mass x Dt x Cp, liquid
0
-20
-40
-60
-80 Heat = mass x Dt x Cp, solid
-100
Time