Table of contents | |
Heat Capacity | |
Solved Examples | |
Heat "Flow" to Thermal Equilibrium | |
Solved Example | |
Measuring Heat "Flow" | |
Constant-Volume Calorimetry | |
Summary |
Figure 12.3.1: Due to its larger mass, a large frying pan has a larger heat capacity than a small frying pan. Because they are made of the same material, both frying pans have the same specific heat.
We can relate the quantity of a substance, the amount of heat transferred, its heat capacity, and the temperature change either via moles (Equation 12.3.3) or mass (Equation 12.3.4):
q = ncpΔT (12.3.3)
where
where
Both Equations 12.3.3 and 12.3.4 are under constant pressure (which matters) and both show that we know the amount of a substance and its specific heat (for mass) or molar heat capacity (for moles), we can determine the amount of heat, q, entering or leaving the substance by measuring the temperature change before and after the heat is gained or lost.
Table 12.3.1 Specific Heats of Common Substances at 25 °C and 1 bar
Example 1: A flask containing 8.0 × 102g of water is heated, and the temperature of the water increases from 21°C to 85°C. How much heat did the water absorb?
Ans: To answer this question, consider these factors:
The specific heat of water is 4.184 J/g °C (Table 12.3.1), so to heat 1 g of water by 1 °C requires 4.184 J. We note that since 4.184 J is required to heat 1 g of water by 1 °C, we will need 800 times as much to heat 800 g of water by 1 °C. Finally, we observe that since 4.184 J are required to heat 1 g of water by 1 °C, we will need 64 times as much to heat it by 64 °C (that is, from 21 °C to 85 °C).
This can be summarized using Equation 12.3.4:
Because the temperature increased, the water absorbed heat and q is positive.
Note that the relationship between heat, specific heat, mass, and temperature change can be used to determine any of these quantities (not just heat) if the other three are known or can be deduced.
Example 2: A piece of unknown metal weighs 348 g. When the metal piece absorbs 6.64 kJ of heat, its temperature increases from 22.4 °C to 43.6 °C. Determine the specific heat of this metal (which might provide a clue to its identity).
Ans: Since mass, heat, and temperature change are known for this metal, we can determine its specific heat using Equation 12.3.4:
q = mcsΔT = mcs(Tfinal − Tinitial)
Substituting the known values:
6,640J = (348g) cs (43.6−22.4)°C
Solving:
Comparing this value with the values in Table 12.3.1, this value matches the specific heat of aluminum, which suggests that the unknown metal may be aluminum.
Example 3: A piece of unknown metal weighs 217 g. When the metal piece absorbs 1.43 kJ of heat, its temperature increases from 24.5 °C to 39.1 °C. Determine the specific heat of this metal, and predict its identity.
Ans: c = 0.45J/g°C; the metal is likely to be iron from checking Table 12.3.1.
Example 4: A home solar energy storage unit uses 400 L of water for storing thermal energy. On a sunny day, the initial temperature of the water is 22.0°C. During the course of the day, the temperature of the water rises to 38.0°C as it circulates through the water wall. How much energy has been stored in the water? (The density of water at 22.0°C is 0.998 g/mL.)
Passive solar system. During the day (a), sunlight is absorbed by water circulating in the water wall. At night (b), heat stored in the water wall continues to warm the air inside the house.
Given: volume and density of water and initial and final temperatures
Asked for: amount of energy stored
Strategy: (a) Use the density of water at 22.0°C to obtain the mass of water (m) that corresponds to 400 L of water. Then compute ΔT for the water.
(b) Determine the amount of heat absorbed by substituting values for m, cs, and ΔT into Equation 12.3.1.
Ans: (a) The mass of water is
The temperature change (ΔT) is 38.0°C − 22.0°C = +16.0°C.
(b) From Table 12.3.1, the specific heat of water is 4.184 J/(g•°C). From Equation 12.3.4, the heat absorbed by the water is thus
Both q and ΔT are positive, consistent with the fact that the water has absorbed energy.
Some solar energy devices used in homes circulate air over a bed of rocks that absorb thermal energy from the sun. If a house uses a solar heating system that contains 2500 kg of sandstone rocks, what amount of energy is stored if the temperature of the rocks increases from 20.0°C to 34.5°C during the day? Assume that the specific heat of sandstone is the same as that of quartz (SiO2) in Table 12.3.1
12.3.
Ans: 2.7 × 104kJ
Even though the mass of sandstone is more than six times the mass of the water in Example 12.3.1, the amount of thermal energy stored is the same to two significant figures.
When two objects initially at different temperatures are placed in contact, we can use Equation 12.3.7 to calculate the final temperature if we know the chemical composition and mass of the objects.
Example: If a 30.0 g piece of copper pipe at 80.0°C is placed in 100.0 g of water at 27.0°C, what is the final temperature? Assume that no heat is transferred to the surroundings.
Given: mass and initial temperature of two objects
Asked for: final temperature
Strategy: Using Equation 12.3.7 and writing ΔT = Tfinal−Tinitial for both the copper and the water, substitute the appropriate values of m, cs , and Tinitial into the equation and solve for Tfinal.
Ans: We can adapt Equation 12.3.7 to solve this problem, remembering that ΔT = Tfinal−Tinitial:
[mcs(Tfinal−Tinitial)]Cu + [mcs(Tfinal−Tinitial)]H2O = 0
Substituting the data provided in the problem and Table 12.3.1 gives
Tfinal (430 J/(g.ºC)) = 12,224 J = 28.4oC
Tfinal = 28.4ºC
Figure 12.3.2: In a calorimetric determination, either (a) an exothermic process occurs and heat, q, is negative, indicating that thermal energy is transferred from the system to its surroundings, or (b) an endothermic process occurs and heat, q, is positive, indicating that thermal energy is transferred from the surroundings to the system.
The amount of heat absorbed or released by the calorimeter is equal in magnitude and opposite in sign to the amount of heat produced or consumed by the reaction.
Figure 12.3.3: A Coffee-Cup Calorimeter. This simplified version of a constant-pressure calorimeter consists of two Styrofoam cups nested and sealed with an insulated stopper to thermally isolate the system (the solution being studied) from the surroundings (the air and the laboratory bench). Two holes in the stopper allow the use of a thermometer to measure the temperature and a stirrer to mix the reactants.
Figure 12.3.4: In a simple calorimetry process, (a) heat, q, is transferred from the hot metal, M, to the cool water, W, until (b) both are at the same temperature.
Example 1: A 360-g piece of rebar (a steel rod used for reinforcing concrete) is dropped into 425 mL of water at 24.0 °C. The final temperature of the water was measured as 42.7 °C. Calculate the initial temperature of the piece of rebar. Assume the specific heat of steel is approximately the same as that for iron (Table T4), and that all heat transfer occurs between the rebar and the water (there is no heat exchange with the surroundings).
Ans: The temperature of the water increases from 24.0 °C to 42.7 °C, so the water absorbs heat. That heat came from the piece of rebar, which initially was at a higher temperature. Assuming that all heat transfer was between the rebar and the water, with no heat “lost” to the surroundings, then heat given off by rebar = −heat taken in by water, or:
qrebar = −qwater
Since we know how heat is related to other measurable quantities, we have:
(c × m × ΔT)rebar = −(c × m × ΔT)water
Letting f = final and i = initial, in expanded form, this becomes:
crebar × mrebar × (Tf,rebar − Ti,rebar) = −cwater × mwater × (Tf,water−Ti,water)
The density of water is 1.0 g/mL, so 425 mL of water = 425 g. Noting that the final temperature of both the rebar and water is 42.7 °C, substituting known values yields:
Solving this gives Ti,rebar 248 °C, so the initial temperature of the rebar was 248 °C.
Example 2: A 248-g piece of copper is dropped into 390 mL of water at 22.6 °C. The final temperature of the water was measured as 39.9 °C. Calculate the initial temperature of the piece of copper. Assume that all heat transfer occurs between the copper and the water.
Ans: The initial temperature of the copper was 335.6 °C.
Example 3: A 248-g piece of copper initially at 314 °C is dropped into 390 mL of water initially at 22.6 °C. Assuming that all heat transfer occurs between the copper and the water, calculate the final temperature.
Ans: The final temperature (reached by both copper and water) is 38.8 °C.
This method can also be used to determine other quantities, such as the specific heat of an unknown metal.
Example 4: A 59.7 g piece of metal that had been submerged in boiling water was quickly transferred into 60.0 mL of water initially at 22.0 °C. The final temperature is 28.5 °C. Use these data to determine the specific heat of the metal. Use this result to identify the metal.
Ans: Assuming perfect heat transfer, heat given off by metal = −heat taken in by water, or:
qmetal = −qwater
In expanded form, this is:
cmetal × mmetal × (Tf,metal − Ti,metal) = −cwater × mwater × (Tf,water − Ti,water)
Noting that since the metal was submerged in boiling water, its initial temperature was 100.0 °C; and that for water, 60.0 mL = 60.0 g; we have:
(cmetal)(59.7g) (28.5°C − 100.0°C) = −(4.18J/g°C) (60.0g) (28.5°C − 22.0°C)
Solving this:
Comparing this with values in Table T4, our experimental specific heat is closest to the value for copper (0.39 J/g °C), so we identify the metal as copper.
Example 5: A 92.9-g piece of a silver/gray metal is heated to 178.0 °C, and then quickly transferred into 75.0 mL of water initially at 24.0 °C. After 5 minutes, both the metal and the water have reached the same temperature: 29.7 °C. Determine the specific heat and the identity of the metal. (Note: You should find that the specific heat is close to that of two different metals. Explain how you can confidently determine the identity of the metal).
Ans: When we use calorimetry to determine the heat involved in a chemical reaction, the same principles we have been discussing apply. The amount of heat absorbed by the calorimeter is often small enough that we can neglect it (though not for highly accurate measurements, as discussed later), and the calorimeter minimizes energy exchange with the surroundings. Because energy is neither created nor destroyed during a chemical reaction, there is no overall energy change during the reaction. The heat produced or consumed in the reaction (the “system”), qreaction, plus the heat absorbed or lost by the solution (the “surroundings”), qsolution, must add up to zero:
qreaction + qsolution = 0 (12.3.10)
This means that the amount of heat produced or consumed in the reaction equals the amount of heat absorbed or lost by the solution:
qreaction = −qsolution (12.3.11)
This concept lies at the heart of all calorimetry problems and calculations. Because the heat released or absorbed at constant pressure is equal to ΔH, the relationship between heat and ΔHrxn is
ΔHrxn = qrxn = −qcalorimater = −mcsΔT (12.3.12)
The use of a constant-pressure calorimeter is illustrated in Example 12.3.7
Example 6: When 5.03 g of solid potassium hydroxide are dissolved in 100.0 mL of distilled water in a coffee-cup calorimeter, the temperature of the liquid increases from 23.0°C to 34.7°C. The density of water in this temperature range averages 0.9969 g/cm3. What is ΔHsoln (in kilojoules per mole)? Assume that the calorimeter absorbs a negligible amount of heat and, because of the large volume of water, the specific heat of the solution is the same as the specific heat of pure water.
Given: mass of substance, volume of solvent, and initial and final temperatures
Asked for: ΔHsoln
Strategy: (a) Calculate the mass of the solution from its volume and density and calculate the temperature change of the solution.
(b) Find the heat flow that accompanies the dissolution reaction by substituting the appropriate values into Equation 12.3.1.
(c) Use the molar mass of KOH to calculate ΔHsoln.
Ans: (a) To calculate ΔHsoln, we must first determine the amount of heat released in the calorimetry experiment. The mass of the solution is
The temperature change is (34.7°C − 23.0°C) = +11.7°C.
(b) Because the solution is not very concentrated (approximately 0.9 M), we assume that the specific heat of the solution is the same as that of water. The heat flow that accompanies dissolution is thus
qcalorimater = mcsΔT
= 5130J
= 5.13kJ
The temperature of the solution increased because heat was absorbed by the solution (q > 0). Where did this heat come from? It was released by KOH dissolving in water. From Equation 12.3.1, we see that
ΔHrxn = −qcalorimeter = −5.13kJ
This experiment tells us that dissolving 5.03 g of KOH in water is accompanied by the release of 5.13 kJ of energy. Because the temperature of the solution increased, the dissolution of KOH in water must be exothermic.
(c) The last step is to use the molar mass of KOH to calculate ΔHsoln - the heat associated when dissolving 1 mol of KOH:
Example 7: A coffee-cup calorimeter contains 50.0 mL of distilled water at 22.7°C. Solid ammonium bromide (3.14 g) is added and the solution is stirred, giving a final temperature of 20.3°C. Using the same assumptions as in Example 12.3.7 , find ΔHsoln for NH4Br (in kilojoules per mole).
Ans: 16.6 kJ/mol
Figure 12.3.4: A Bomb Calorimeter. After the temperature of the water in the insulated container has reached a constant value, the combustion reaction is initiated by passing an electric current through a wire embedded in the sample. Because this calorimeter operates at constant volume, the heat released is not precisely the same as the enthalpy change for the reaction.
Example 1: The combustion of 0.579 g of benzoic acid in a bomb calorimeter caused a 2.08°C increase in the temperature of the calorimeter. The chamber was then emptied and recharged with 1.732 g of glucose and excess oxygen. Ignition of the glucose resulted in a temperature increase of 3.64°C. What is the ΔHcomb of glucose?
Given: mass and ΔT for combustion of standard and sample
Asked for: ΔHcomb of glucose
Strategy: (a) Calculate the value of qrxn for benzoic acid by multiplying the mass of benzoic acid by its ΔHcomb. Then use Equation 12.3.1 to determine the heat capacity of the calorimeter (Cbomb) from qcomb and ΔT.
(b) Calculate the amount of heat released during the combustion of glucose by multiplying the heat capacity of the bomb by the temperature change. Determine the ΔHcomb of glucose by multiplying the amount of heat released per gram by the molar mass of glucose.
Ans: (a) The first step is to use Equation 12.3.1 and the information obtained from the combustion of benzoic acid to calculate Cbomb. We are given ΔT, and we can calculate qcomb from the mass of benzoic acid.
From Equation 12.3.1,
(b) According to the strategy, we can now use the heat capacity of the bomb to calculate the amount of heat released during the combustion of glucose:
qcomb = −CbombΔT = (−7.34kJ/oC)(3.64oC) = −26.7kJ
Because the combustion of 1.732 g of glucose released 26.7 kJ of energy, the ΔHcomb of glucose is
This result is in good agreement (< 1% error) with the value of ΔHcomb = −2803kJ/mol that calculated using enthalpies of formation.
1. What is heat capacity and how is it related to thermal equilibrium? |
2. How can heat flow be measured? |
3. What is constant-volume calorimetry? |
4. How is heat capacity related to enthalpy? |
5. How can heat capacity be calculated? |
|
Explore Courses for UPSC exam
|