CHEM161 Experiment 7: Calorimetry

Introductio
n
Calorimetry is the science of measuring heat flow, and heat is defined as thermal energy
flowing from an object at a higher temperature to one at a lower temperature. For example, if a
chunk of metal at room temperature is placed in a beaker of boiling water, the metal will
absorb heat from the water until it is at the same temperature as the boiling water.
Scientists also often study the heat associated with different physical and chemical changes.
Ideally, the heat changes resulting from physical and chemical phenomena can be harnessed to
do work. For example, the burning of gasoline and fossil fuels can be used to run our
automobiles and heat our houses. However, in some cases, the heat associated with some
processes is transferred to the environment for example, traditional incandescent light bulbs
use almost as much !or maybe more" electricity to produce heat rather than light.
#ost physical and chemical changes are either exothermic or endothermic. Exothermic
reactions release energy or heat to increase the temperature of the surroundings thus, the
surroundings are hotter after an exothermic change. For example, nitroglycerine exploding is
an extremely exothermic reaction. Endothermic reactions absorb energy or heat to decrease
the temperature of the surroundings thus, the surroundings are colder after an endothermic
change. For example, cold packs used to relieve swelling joints or muscles often use chemicals
that absorb heat when mixed, so the packs feel cold.
$hen a reaction is carried out under constant pressure, the heat of a reaction is defined as the
enthalpy change for the reaction !H". Since most reactions occur under constant atmospheric
pressure, the heat of a reaction is e%ual to H, which is generally reported in units of kilojoules
!k&" per mole of the reactants and products as shown in the balanced thermochemical e%uation.
For example, the reaction between hydrogen gas and oxygen gas to produce water is
represented by the following thermochemical e%uation'
( H((g) ) *((g) ( H(*(l) H + ,-./.0 k& 1/2
3ote that the sign of the enthalpy change indicates whether the reaction is exothermic or
endothermic. If H is negative, the reaction is exothermic. Since H for the formation of
water is negative, it is exothermic, so this reaction releases heat. 4he surroundings become
hotter, which is observed as an increase in temperature.
For endothermic changes, H is positive. Heat is absorbed from the surroundings, and because
the surroundings lose heat, they become colder, which is observed as a decrease in
temperature. For example, solid ammonium chloride dissolving in water is an endothermic
process which is represented by the following thermochemical e%uation'
3H56l(s) 3H5
)
(aq) ) 6l

(aq) H + )/5.7 k& 1(2

4o measure the enthalpy change for a chemical reaction in the lab, a calorimeter is used. 8
calorimeter is any well,insulated apparatus that can hold the reactants and products, so the
amount of heat that is absorbed or released by a reaction or process can be measured.
4hus, the heat of the reaction (q) can be determined by measuring the temperature change
!T Tfinal ! Tinitial" for the calorimeter contents and using their specific heat9i.e., the heat
re%uired to raise the temperature of / gram of the substance by /6.
q specific heat mass T 1:2
3ote that the sign for the % is determined by the change in temperature !4". If the temperature
increases, T is positive, and q is positive, indicating the calorimeter contents a"sor"ed
heat. 4hus, the reaction must have released heat, so it is exothermic. If the temperature
decreases, T is negative, and q is negative, indicating the calorimeter contents lost heat.
4hus, the reaction must have gained heat, so it is endothermic.
In this experiment, the calorimeter used will consist of two nested Styrofoam coffee cups with
a cover and a thermometer !see Figure below".
However, instead of a glass thermometer, the ;ernier <ab=uest system will be used to measure
and record the temperature change for the calorimeter contents.
Ideally, the calorimeter is so well insulated, that all of the heat gained or lost during the
reaction is completely contained within the calorimeter. In reality, the coffee,cup calorimeter is
not a perfect insulator, so it will actually absorb and lose heat however, in this experiment, the
heat absorbed or lost by the calorimeter is often negligible given the temperatures measured.
Heat transfer does not occur instantaneously, so using a calorimeter to determine the enthalpy
change re%uires measuring the temperature of the calorimeter contents as the physical or
chemical change occurs and for several minutes afterwards. 4he maximum temperature
reached by the calorimeter contents can rarely be measured directly because of drastic
temperature fluctuations near the probe or heat lost at the time of mixing. If the contents are
mixed uniformly while data is recorded, the contents should e%uilibrate at a consistent rate.
4hus, the time,temperature data can be plotted, and the resulting regression line can be
extrapolated to the time of mixing to get the maximum or final temperature. 4he initial and
final temperatures can then be used to calculate the change in temperature !4" and the
resulting heat gained or lost, as shown in the example below'
Example for #etermining the Enthalpy Change (H) for a $eutrali%ation &eaction'
$hen /.->> g of solid potassium hydroxide is added to (-.>> m< of (.>/># hydrobromic
acid at ((.-?6 in a coffee,cup calorimeter, the temperature of the resulting solutions is
measured and recorded for /@> s. !4he density of the hydrobromic acid is /./-7 gAm<, and
Calculating
the Heat
Absorbed
the specific heat of the solution is :..> &AgB?6." 4he temperature data is plotted with respect
to time, and a regression line for the peak temperature and subse%uent readings is obtained.
(igure )' Temperature versus Time *lot for the H+r(aq) , -.H(s) &eaction
4he e%uation for the regression line in the plot shows the y,intercept is 57./(-?6, which is
rounded to 57./?6 to reflect the accuracy of the thermometers used9i.e., the thermometers
used to collect the data for the plot are only accurate to t>./?6, so the final temperature is
also only accurate to t>./?6.
4he initial and final temperatures of the hot water and the cold water were measured, so the
change in temperature for each can be calculated as shown below'
4 + 57./?6 C ((.-?6 + (0.0?6 152
4he heat absorbed by the solution can be calculated using the specific heat of resulting
solution,
6 g
& :..>

, the volume and density of the hydrobromic acid along with the mass of
the solid sodium hydroxide to get the total mass of solution, and the change in temperature.
heat a"sor"ed "y the solution qsol/n cs 0 msoln 0 T 1-2

%soln +

,
_

6 g
& :..>
1
]
1

,
_

+ D*H g /.->>
m<
g /./-7
HEr" m< !(-.>>
!(0.0?6" + (777.:- &
3ote that the heat calculated is not yet rounded to the correct significant figures !sig figs"
but must eventually be rounded to : sig figs, as indicated by underlining the first three
digits.
8ssuming the calorimeter is a perfectly insulator and absorbs no heat itself, the heat
absorbed by the solution should e%ual the heat lost by the reaction'
qsoln !qrxn 102
Fearranging G%uation 102 results in %rxn + !%soln + !(777.:- &
Gnthalpy changes are generally reported in kilojoules per mole !k&Amol" of a reactant or
product for example, in acid,base neutraliHation reactions, like the example above, the heat
of neutraliHation !Hneut" is generally reported in kilojoules per mole of water produced
!k&Amol H(*".
4o determine the number of moles of water produced, the limiting reactant must be
determined using the balanced chemical e%uation'
HEr(aq) ) D*H(aq) H(*!l" ) DEr(aq)
* H mol >.>(0.:5/
* H mol D*H mol
(
(
D*H mol D*H g -0./>@
D*H g /.->>
* H mol >.>->(-
* H mol
<
HEr mol (.>/>
(
(
HEr mol
< >.>(->>
4hus, D*H is the limiting reactant, and >.>(0.: moles of H(* are produced. 4he heat of
neutraliHation !Hneut" for the reaction can then be calculated as follows'
* H k&Amol //( ,
& />>>
k& /
* H mol >.>(0.:5/
& (777.:- ,
(
(

4hus, rounded to the correct number of sig figs, the heat of neutraliHation !Hneut" for
hydrobromic acid reacting with solid potassium hydroxide is ,//( k&Amol of water
produced.
4he heat for any reaction can be calculated in the same way, by measuring and plotting the
temperature change for the system. 8gain, the regression line is extrapolated to the time of
mixing to obtain the final temperature and calculate the overall temperature change.
In this experiment, the specific heat is 1.23 45g06C for the resulting solutions in both reactions,
H6l(aq),3a*H(aq) and H3*:(aq),3a*H(aq). 4hus, the heat absorbed or released by the
calorimeter contents is calculated as follows'
%soln +

,
_

6 g
& :..>

,
_

solution of
mass total
!4solution" 1.2
4he initial temperature is taken as the average temperature of the reactants before mixing
assuming e%ual amounts of reactants are mixed, and the final temperature is obtained by
plotting the temperature change for the calorimeter contents as shown in Figure / on the
previous page. 4he mass of the solution is measured directly by weighing the calorimeter with
and without the solution and taking the difference.
4he enthalpy change for both acid,base neutraliHation reactions !Hneut" will be reported in units
of kilojoules per mole !k&Amol" of water produced. 4hus, the amount of water that can be
produced given the amounts of each reactant must be calculated, and Hneut is calculated as
follows'
Hneut
produced 7ater of moles of 8
reaction
q
1@2
In this experiment, the heat of neutraliHation for the reaction between hydrochloric acid and
sodium hydroxide will be determined experimentally using a coffee,cup calorimeter. In
addition, the heat of neutraliHation for the reaction between nitric acid and sodium hydroxide
will be determined experimentally in the same way.
4he resulting salt solutions for both neutraliHation reactions !H6l,3a*H and H3*:,3a*H" will
contain a sufficient number of ions to change the specific heat to be slightly lower than waterIs.
The specific heat used for each solution is
C g
4 1.23

.
Procedure
Heats o
!eutrali"
#ation
$A%E&' P(ECA)&I*!$: !a*H+ H!*,-a./+ and HCl-a./ are toxic and corrosive and can
all cause chemical burns upon contact with skin. NaOH can damage eyes on contact. Any acid
or base spilled on your skin or clothing must be rinsed immediately with water or !" minutes.
#norm your instructor o an acid or base spills.
9tudents 7ill 7or: in pairs to complete the experiment.
Experimental #etermination of the Hneut for HCl-a./!$a.H-a./ and for H$.1-a./!
$a.H-a./
/. *btain four Styrofoam coffee cups !to make two sets of nested calorimeters" and one
lidAcover. Jse a pencil to mark one calorimeter K/ and the second calorimeter K(. Jse a
centigram or milligram "alance to weigh empty calorimeter K/ with the cover, and record
the mass.
(. 6heck out a ;ernier <ab=uest system from the stockroom.
$ote' The ;ernier <a"=uest systems are expensive and not covered "y
standard la" "rea:age fees. The displays can "e easily damaged "y chemical
spills and must "e :ept as far a7ay as possi"le from any chemicals. 9tudents
7ill "e charged the full cost to replace damaged <a"=uest systems in
addition to any la" fees already paid.
:. Fecord the molarity of the 3a*H solution. Jse the self,Heroing buret to measure out ->.>>
m< of 3a*H solution directly into calorimeter K/. Fecord the molarity of the hydrochloric
acid. Jse the self,Heroing buret to measure out ->.>> m< of hydrochloric acid directly into
calorimeter K(.
5. Llug the two temperature probes into M6H/ and 6H(N of the <ab=uest. 6onnect and plug
$a0e the
1ab2uest
3ata
*btaining
the &
inal
using
1oggerPro
Adding &itles
to the Plot
and 3ata
&able
Printing the
3ata &able
and4or Plot
in the <ab=uestIs 86 adaptor. 4urn on the <ab=uest by pressing the Lower button on the
top left corner !surrounded by a blue light". 4he system will take a few minutes to boot up.
-. Swirl the 3a*H solution in calorimeter K/, cover it with the lid, put the M6H/N probe
through the lid and into the 3a*H solution in calorimeter K/. #easure the temperature of
the solution until the temperature remains constant for at least :> seconds. Fecord the
temperature.
0. 4he probes should be automatically detected, so when the screen comes on, it should
display two temperatures. *n the right hand side are three windows' >ode, &ate, and
<ength. 4he #ode should be M4ime EasedN the Fate should be M( samplesAsN and the
<ength should be M/@>.> sN. 4o make changes use the stylus !attached to the string" to tap
on the appropriate window to correct the setting.
$ote' The tip of the <a"=uest pro"es are sharp and can easily pierce the
9tyrofoam cups. +e sure to :eep the tip su"merged in 7ater or solution "ut do not
touch the "ottom of the 9tyrofoam cup 7ith the pro"e.
.. Llace the M6H(N probe into the hydrochloric acid solution in calorimeter K(. !OonIt use the
lid for the acid." #easure the temperature of the hydrochloric acid until the temperature
remains constant for at least :> seconds. Fecord the temperature. Jnplug the M6H(N probe.
@. <ift the lid and probe then press on the collect button, , to collect the temperature
of the 3a*H solution in calorimeter K/. =uic:ly "ut carefully transfer the acid to
calorimeter K/, replace the lid and probe, and swirl the solution to insure complete mixing.
4he <ab=uest will record the temperature of the solutions in calorimeter K/ for /@> s and
plot the data on the screen.
7. 8fter /@> s of data, save the data to your thumbAFlash drive by tapping on the MFileN
dropdown menu and choose MSaveN. 6lick on the 3ame box on the top of the screen, and
enter the file name. 4he .qm"l format is the file type for the ;ernier <oggerLro software.
4o save your data in your thumbAFlash drive, tap on the MFileN dropdown menu and choose
MSaveN, then tap on the ?9+ icon, and type in the file name. 6hoose a descriptive and
distinct filename for each trial.
/>. $eigh and record the mass of calorimeter K/ with the solution and cover.
//. 4he <oggerLro software is installed on any student computer at S666. Fetrieve the data
from the thumb/Flash drive by double,clicking on the .%mbl file, and the <oggerLro
software should open automatically. !If it does not, launch the <oggerLro software in the
Lhysics folder in 8ll Lrograms from the Start menu., then open the file." 4he <oggerLro
software should display both the data table and the plot.
/(. Llace the cursor on any point in the plot, and it will display the time and temperature. Jse
the data table to determine when the temperature peaks and begins to fall, and place the
cursor at that point. Lress down on the left mouse button and drag the cursor all the way to
the right to highlight the points recorded after the temperature peaks. 4ap on the Mlinear fitN
icon, , and a text box will appear. #ove the box if it shows up on top of your points.
4he value of the y,intercept is the final temperature, 4final, of the water in the calorimenter.
/:. Oouble,click on the graph to open the Praph *ptions window, and enter a 4itle for the plot
!e.g. M4emperature 6hange for the 6alorimeterN". 4o change the title of the Oata 4able,
click on the title, and a Oata Set *ptions window will open.
/5. For a record of the final temperature for the first trial of the H6l,3a*H heat of
neutraliHation determination, print a copy of the graph showing an appropriate title and the
regression line data with the y,intercept. Have your instructor approve your graph.
/-. Oispose of the contents of calorimeter K/ in the sink, then wash and dry both calorimeters
completely. $ash and dry the cover. Jse your water bottle to completely rinse the
<ab=uest probes with OI water, then dry each with a Dimwipe.
/0. Fepeat steps (,@ for 4rial K( for hydrochloric acid.
/.. Fepeat steps (,@ for 4rials K/ and K( for the H3*:(aq),3a*H(aq) reaction.
/@. <oggerLro allows the data table and graph to be printed together or separately. Follow the
instructions below for each'
To print "oth the data ta"le and graph, click on the File dropdown menu, choose
Lage Setup, and change *rientation to <andscape, then press *D. 3ext, type 6trl)p or
click on the File dropdown menu and choose LrintQ. 4he Lrinting *ptions window
should open. 6lick on the Lrint Footer option, and type your name and your partnerIs
name, then *D.
To print @ust the graph, click on the File dropdown menu, choose Lage Setup, and
change *rientation to <andscape, then press *D. 3ext, on the File dropdown menu,
choose Lrint PraphQ, and the Lrinting *ptions window should open. 6lick on the Lrint
Footer option, and type your name and your partnerIs name, then *D.
To print @ust the data ta"le, click on the File dropdown menu, choose Lrint Oata
4ableQ, and the Lrinting *ptions window should open. 6lick on the Lrint Footer
option, and type your name and your partnerIs name, then *D.
/7. 6lick on the numbers on the y,axis until the Format 8xis window appears. 6lick on the
Scale tab. 6hange the #inimum from Hero to be just under the lowest temperature, and if
necessary, change the #aximum to be just above the trendlineAregression line.
#ispose of the inside cup in each calorimeter in the trash, and return the outside cup to
the stoc:room. Aash and dry all glass7are used. Ta:e a 7et paper to7el, and 7ipe do7n
your entire 7or: area.
#BTB B$B<C9I9 B$# CB<C?<BTI.$9
8verage the initial temperature of the acid and base for each trial.
Jse <ogger*ro to prepare plots for the temperature change for the remaining neutraliHation
reactions between H6l(aq),3a*H(aq) and H3*:(aq),3a*H(aq).
For each plot,
Lrovide a descriptive title for the plot.
<abel each axis !including units".
Include a trendAregression line, showing the e%uation for the line with the y,intercept.
?se
C g
4 1.23

for the specific heat of the salt solutions resulting from "oth neutrali%ation
reactions (HCl!$a.H and H$.1!$a.H).
For each trial, calculate the heat absorbed by the solution then calculate the heat released by the
reaction using G%uations .,@. 3ext, calculate the number of moles of water produced using the
amount of each acid and base used for each trial. 6alculate the enthalpy of neutraliHation
!Hneut" for each reaction in k& per mole of water produced.
Experiment 7: Calorimetry 3ame'
RRRRRRRRRRRRRRRRRRRRRRRRRR
Pre"1aboratory Assignment Section 3umber'
RRRRRRRRRRRRRRRRRR
/. Lredict the products !including physical states", and write the total ionic and net ionic e%uations for the
reaction between hydrochloric acid and a%ueous sodium hydroxide.
balanced
chemical
e%uation'
total
ionic
e%uation'
net ionic
e%uation'
(. Lredict the products !including physical states", and write the total ionic and net ionic e%uations for the
reaction between nitric acid and a%ueous sodium hydroxide.
balanced
chemical
e%uation'
total
ionic
e%uation'
net ionic
e%uation'
:. Piven the net ionic e%uations for the reactions above, explain if the enthalpy of neutraliHation !Hneut"
should be the same for both reactions.
5. Eriefly explain why the Mfinal temperatureN of the calorimeter contents is not simply the last or highest
temperature recorded during a calorimetry experiment.
Experiment 7: Calorimetry 3ame'
RRRRRRRRRRRRRRRRRRRRRRRRRRRRRRRR
Lartner'
RRRRRRRRRRRRRRRRRRRRRRRRRRRRRRR
#BTB
#ass of empty 6alorimeter K/ ) cover' RRRRRRRRRRRRRRRRRRRRRRRRRRRRRRRR
Experimental #etermination of the Hneut for HCl-a./!$a.H-a./ and for H$.1-a./!$a.H-a./
sodium hydroxide hydrochloric acid nitric acid
#olarity of the solution
;olume of solution used
in each trial
D3.33 m< D3.33 m< D3.33 m<
HCl-a./!$a.H-a./ 4rial K/ 4rial K(
Initial 4emperature of H6l!a%"
Initial 4emperature of 3a*H!a%"
8verage Initial 4emperature
#ass of 6alorimeter K/ ) solution
) cover !after reaction"
#ass of empty 6alorimeter K/ ) cover
!from part 8"
#ass of solutionS
S Jse #ass of empty 6alorimeter K/) cover from Lart 8 to calculate
H$.1-a./!$a.H-a./ 4rial K/ 4rial K(
Initial 4emperature of H3*:!a%"
Initial 4emperature of 3a*H!a%"
8verage Initial 4emperature
#ass of 6alorimeter K/ ) solution
!after reaction"
#ass of solutionS
SJse #ass of empty 6alorimeter K/) cover from Lart 8 to calculate
For each trial, attach the Oata 4able obtained using the ;ernier <ab=uest system, along with the titled
graph with labeled axes that shows the regression line and the y,intercept with the maximum
temperature !4final".
Show calculations for each step of the H6l!a%",3a*H!a%" and the H3*:!a%",3a*H!a%" neutraliHation
reactions in your lab notebook.
&esults Ta"le to #etermine Heat of $eutrali%ation for the HCl(aq)!$a.H(aq) &eaction
4rial K/ 4rial K(
#aximum 4emperature
!y,intercept" from the plot
6hange in 4emperature !4"
%solution !in k&"
%reaction !in k&"
K of moles of H(* produced
Hneut !in k&Amol H(*"
8verage Hneut !in k&Amol H(*"
&esults Ta"le to #etermine Heat of $eutrali%ation for the H$.1(aq)!$a.H(aq) &eaction
4rial K/ 4rial K(
#aximum 4emperature
!y,intercept" from the plot
6hange in 4emperature !4"
%solution !in k&"
%reaction !in k&"
K of moles of H(* produced
Hneut !in k&Amol H(*"
8verage Hneut !in k&Amol H(*"
CHEM 161 Experiment 7: Calorimetry Post"1aboratory
2uestions
*ost!<a"oratory Calculations to include in the (ormal <a" &eport
/. $rite the net ionic e.uation for the reaction between hydrochloric acid and a%ueous sodium
hydroxide, then calculate the heat of neutraliHation !Hneut" for the reaction using the standard
enthalpies of formation !

f
H " in the 8ppendix of the textbook for each reactant and product.
Oo the same for the reaction between nitric acid and a%ueous sodium hydroxide.
(. 6alculate the percent error for your average experimental a0erage Hneut or each reaction
using the following formula'
E error
)33E
value true
F value true value al experiment F

*ost!<a"oratory =uestions to address in the #iscussion 9ection of the (ormal <a" &eport
/. Jse the observed temperature change to explain if acid,base neutraliHation reactions are
endothermic or exothermic. Gxplain if the sign for the calculated heat of neutraliHation !Hneut"
should be positive or negative based on the observed temperature change.
(. 8re the heats of neutraliHation for the reaction between hydrochloric acid and a%ueous sodium
hydroxide and for the reaction between nitric acid and a%ueous sodium hydroxide the sameT
Gxplain why. $ould you expect the heats of neutraliHation for the reactions to be the same if
barium hydroxide were used instead of sodium hydroxideT Gxplain why.
:. How would the temperature change and the calculated heats of neutraliHation vary if the
concentrations of the acids and the base used in this experiment were doubledT Gxplain.
5. $ould the temperature change and the heats of neutraliHation vary if the concentrations
remained the same but the volume of each acid and base used in this experiment was cut in
halfT Gxplain.
-. If your percent error was greater than -U, discuss possible sources of error in the experiment.
If you carried out more than two trials andAor omitted data from a trial to calculate your
average, discuss why this was necessary. !Lrovide specific sources of experimental error that
could have caused your incorrectly high or incorrectly low experimental results. Oo not discuss
calculation errors."
$ote' Cour formal la" report should include the four graphs (t7o each for the acid!"ase
neutrali%ation reactions), each 7ith a descriptive title and la"eled axes. In addition,
your report should also include the purpose, procedure, data, calculations, results in
summary ta"les, discussion, and conclusion.