Ramy Chaoul

BOMB CALORIMETRY: DETERMINATION OF THE HEAT OF COMBUSTION AND THE STANDARD ENTHALPY OF FORMATION OF GLUCOSE

Course: Chem 220 Name: Ramy Chaoul Instructor: Dr. Samar Sadek Group (C)

Date: 25/02/2013
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Ramy Chaoul

Abstract:
The purpose of this experiment is to measure the heat of combustion of glucose using a constantvolume bomb calorimeter; where heat causes an increase or rise of the temperature by the calorimeter is which is evaluated and used to calculate the change of energy during combustion. Thus we can use this data to and apply thermodynamic relations to calculate the enthalpy of combustion and the enthalpy of formation of glucose. To determine the specific heat capacity (Cv) of the bomb calorimeter we standardize it by the use of benzoic acid pellets of which the heat capacity (Cv Benzoic acid) is known to and thus enables the determination of the calorimeter heat capacity. We also use the benzoic acid for spiking and triggering glucose combustion. After calibration, we add a certain defined mass of benzoic acid to glucose, and thus glucose combustion is studied. Two sources of heat that cause a rise in temperature are considered as an error to be corrected; the first is the fuse combustion while the second is due to the presence of N2 in the bomb calorimeter. We determine the increase in temperature due to the fuse combustion by weighing the fuse before and after each run; while the nitric oxide in the calorimeter is converted to nitric acid when it reacts with water, and thus to correct for N2 present as part of entrapped air, a titration with standardized base of sodium carbonate is conducted. Our obtained values for Hcombustion and Hoformation are -3855.854 KJ/mol and 609.1805 KJ/mol respectively, with % errors of (13.45%) and (29.79%)respectively.

Ramy Chaoul

Introduction (2):

fig 1: bomb calorimeter(1)

During the combustion of glucose the heat transfer is monitored and measured using a constant volume bomb calorimeter. Each material has a specific enthalpy of combustion, which is the enthalpy change accompanying a complete oxidation of the material to form H2O and CO2 (1) .The combustion reaction is: C6H12O6 + 6O2 6CO2+ 6H2O An enthalpy change that accompanies an isothermal process is not measured directly (i.e., the change of state is not carried out isothermally). Instead the process is carried out adiabatically, using a path composed of 2 steps (2): To start, we measure the experimental process of enthalpy change isothermally by the formula: R1(T0)+R2(T0)+S(T0) P1(T0)+P2(T0)+S(T0) Where Uisothermal= UT0 Where S refers to all parts of the system that is in contact with the reaction medium other than the reactants and products by that we mean that S refers to the stirrer, the calorimeter walls, the water bucket ...etc The determination step is not carried in a single isothermal step because the fall and rise of heat causes it variation, thus the determination is carried adiabatically by 2 steps, where U is a state function that is independent of the used path:
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(1) Adiabatic Process: (from T0 to T1) R1(T0) +R2 (T0) + S (T0) P1(T1)+P2(T1)+S (T1) Ucal (2) Imaginary Process back to the initial temperature(from T1 to T0) P1(T1)+P2(T1)+S(T1) P1(T0)+P2(T0)+S(T0) Uimag with Uisothermal = Ucal + Uimag

But Ucal = qv + W = 0

where we have a constant volume: V =0 then W=pV = 0 where the heat flow in an adiabatic process qv is also = 0.
0

Then, Uisothermal = Uimag = qv + w = Cv T= Cv (T0- T1) = -Cv (T1-T0) where Cv = Cv (S) + Cv (H2O) + Cv (CO2) To determine the heat capacity Cv (of the whole bomb), standardization is applied, where the known heat of combustion of benzoic acid is used in the standardization reaction. To calculate Cv, T (the calorimeter measures the temperature rise), the following equation is used: mbenzoic acid Ubenzoic acid + mfuse Ufuse + meq UN2= -Cv (S) T with: mfuse = mass of fuse combusted (g) meq = milliequivalence = mmol of N2 present at equivalence (mmol)= N(base) x V(base at eq.) Ufuse = -1400.0 cal/g Ubenzoic acid = -6318.0 cal/g T = temperature rise measured by the calorimeter (C) Since the number of moles produced from the combustion of standard material of carbon dioxide and water is different from the number of moles produced upon the combustion of the material under study, we will encounter an error that we will consider as a minimal error, because of the very small mass of the sample used which is 1g, compared with the mass of water in the bucket which is 2000 g, where the masses of the bomb and bucket > 500 g. CV can thus be approximated as being equal to CV (S), and thus the equation becomes: Uisothermal = -Cv (S) (T1-T0) Ideally the situation would be when a change in temperature is solely due to a change in the energy of combustion of glucose. However, the ideal situation is not present in this experiment. A correction is needed for these errors.
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UN2 = -14.1 cal/meq

Ramy Chaoul

The first correction we account for is the change in energy due to the combustion of the fuse used, where two measures of the fuse are conducted one before and one after a calorimeter run in order for us to calculate the mass of the burned wire. The heat correction for fuse combustion is given as 1400 cal/g. The second correction is for the air that enters the bomb and causes a temperature rise, where the N2 present in air is converted to nitric oxide upon reacting with oxygen then into nitric acid upon reacting with the water inside the bomb. We calculate the concentration of nitric oxide by a base titration of the nitric acid HNO3 with standard sodium carbonate NaHCO3 (0.0709 M) and thus we will be able to know the amount of nitrogen gas trapped in the bomb. Methyl orange is used as an indicator. The heat released from this reaction of nitrogen and oxygen is 14.1 cal/meq of HNO3. The third and final correction (1) is for the calculated standard enthalpy of formation from the enthalpy of the combustion reaction, where we neglect the pressure effect on the values of energy and enthalpy. In reality, the effect of pressure changing on the energy and enthalpy is very small relative to the accompanied chemical changes. Thus the equation for glucose becomes: msugar Usugar + m BA UBA + mfuse Ufuse + meq U(N2) = -Cv (s) T

where: mBA = mass of benzoic acid used as spiking material (g) mfuse = mass of fuse combusted (g) meq = milliequivalence = mmol of N2 present at equivalence (mmol) Ufuse = -1400.0 cal/g UN2 = -14.1 cal/meq Ubenzoic acid = -6318.0 cal/g T = the measured temperature rise by the calorimeter (C) After we determine Uglucose, its enthalpy of combustion is calculated using the following thermodynamic relation: Hglucose = Uglucose + (PV) Hglucose = Uglucose + ngasRT with: ngas= change in number of moles of gases (mol) = n nreactants products R = gas constant 8.314 J/mol.K
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T = T0 = temperature of the adiabatic process (C) The standard enthalpy of formation of glucose H0f is determined using: H reaction = H formation of products - H formation of reactants H glucose = 6H0f
(CO2) + 6

H0f

0 (O2) - H f (glucose)

Experimental Plan:
1- The calorimeter should be warmed for 20 min until the jacket temperature is constant and stabilized at 35 C. 2- Cut a 10 cm of Ni alloy wire and weigh it on each run, the wire must be twisted it in a bell-shaped loop with no sharp edges to avoid the cutting of the wire, so that we will attach the loop to the openings at the end of the grip electrodes of the bomb. 3- Weigh a benzoic acid pellet to know its mass, and then transfer it to the sample capsule on the electrode loop, where it is fixed in position using the Ni alloy fuse wire. 4- Add 1 mL of distilled water to the bomb, where it will act as an absorbing agent and thus absorb nitric oxide entrapped in the air and convert it to nitric acid. The sealing ring must be moistened. 5- Use the pressurized oxygen gas to fill the bomb with oxygen at a pressure of 30 atm that should be maintained, release the valve two consecutive times to expel unwanted N2 entrapped in the air. 6- Fill the bucket with 2000 grams of water (at constant temperature 300C) and then place the bucket in the calorimeter so that the bomb calorimeter will be placed in the bucket. 7- Using the specific clamp, lower the bomb and place it in the bucket after attaching the two ignition wires into the sockets on the bombs head and make sure of the complete immersion of the bomb into the bucket. 8- Now we close the calorimeter and press shift start then enter sample ID # followed by the weight of the sample under study. 9- At the process end we press DONE bottom to store the results, where we open the cover to disconnect, and remove the bomb be using the clamp once again.

Ramy Chaoul 10- More water is added to the 1 ml already present in order to wash the bomb where the washings are titrated with 0.0709 N Sodium carbonate for acid correction. 11- The procedure is repeated twice for benzoic acid (standardization), and another two times for glucose (determination), and finally a last time for the unknown sugar determination.

Data:
ID number Mass benzoic acid pellet Mass 10 cm wire Mass remaining fuse Volume Na2CO3 Initial Temperature T temperature rise 0.0001g 0.0001g 0.0001g 0.02 mL 0.00001C 0.00001C

7
1.0125 0.0169 0.0034 3.80 27.7049 2.65477

8 1.0119 0.01603 0.0031 5.10 27.1285 2.65087

Table 1: Standardization by combustion of Benzoic Acid pellets (sample 7 and 8)

ID number Mass benzoic acid Mass sugar in pellet Mass pellet Mass 10cm wire Mass remaining fuse Volume Na2CO3 Initial Temperature T temperature rise 0.0001g 0.0001g 0.0001g 0.0001g 0.0001g 0.02 mL 0.00001C 0.00001oC

9
0.2946 0.6940 0.9696 0.0165 0.0029 1.90 27.3024 1.79823

10 0. 2985 0.6965 0.9874 0.0165 0.0039 4.40 28.7004 1.84897

Table 2: determination by combustion of Benzoic Acid in Mixed pellets (sample 9and 10)

Ramy Chaoul

ID number Mass benzoic acid Mass unknown powder Mass pellet Mass 10cm wire Mass remaining fuse Volume Na2CO3 Initial Temperature T temperature rise 0.0001g 0.0001g 0.0001g 0.0001g 0.0001g 0.02 mL 0.00001C 0.00001oC

11
0.2957 0.6979 0.9656 0.0162 0.0014 2.00 28.2060 1.78447

Table 3: combustion of unknown powder mixed with benzoic acid (sample11)

N.B. Instruments Burette Analytical balance Bomb calorimeter Table 4: uncertainty Uncertainties 0.02ml 0.0001 g 0.00001 0C

Calculation:
CV of the calorimeter

( ) ( ) m fuse = m fuse before firing m fuse after firing. m eq (milliequivalence) = NHNO3 VHNO3 = NNa2CO3 VNa2CO3 = number of millimoles of
HNO3 at equilibrium

Ramy Chaoul

given:

Ubenzoic acid = -6318.0 cal/g U wire = - 1400.0 cal/g U (N2) = -14.1 cal/meq (reference 2)

Sample #7 (standardization): Cv = (-1/T) (mUbenzoic acid+mfuseUfuse+meqU(N2))

= (-1/2.65477) ((0.9985g*-6318cal/g) + (0.0135g*-1400cal/g)+(3.80*0.0709N*-14.1) Then, Cv= 2421.20 cal/0C

Sample # 8:

Cv = (-1/T) (mUbenzoic acid+mfuseUfuse+meqU(N2))

= (-1/2.65087) ((0.9941*-6318cal/g) + (0.0129g*-1400cal/g)+(5.10*0.0709N*-14.1) Then, Cv= 2436.26 cal/0C Average Cv : Cvavg= (Cv71+ Cv74 )/2= 2428.73 cal/0C

Determining the U combustion of glucose:

Uglucose = [ - CvT (mBA UBA + mburned fuse U fuse + meq U(N2) ] / mglucose

Sample #9(determination):
Mass of glucose=0.6940g Mass of benzoic acid=0.2946g Mass of the pellet= 0.9696 g
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%glucose = (0.6940/(0.6940+0.2946))*100=70.20% %benzoic acid = (0.2946/(0.2946+0.6940))*100=29.80% Then, the mass of benzoic acid in the pellet is: mb= mpellet* percentage of benzoic acid= 0.9696*29.80%=0.2889g And the mass of glucose in the pellet is: mg= mpellet* percentage of glucose= 0.9696*70.20%= 0.6807 g using the equation: Uglucose=(1/ mglucose) (-CvT - mUbenzoic acid-mfuseUfuse-meqU(N2) ) =(1/0.6807)(2422.905*1.79823 - 0.2889*-6318 0.0136*-1400 1.90*0.0709*14.1)= -3694.035cal/g

Uglucose( for sample 9 ) = -3694.035cal/g

Total mass 0.0001 g % glucose 0.8 % % benzoic acid 1% M glucose M benzoic acid U glucose 0.9696 70.20% 29.80% 0.6807 g 0.2889g -3694.035cal/g

Table 5: sample 9

Then using the formula: H=U+ (pV)= U+ RTn but, n= 0 so Hcombustion=Uglucose Thus Hcombustion=Uglucose= -3694.035cal/g Then, conversion of the unit of the combustion into joule units: Hm=H M 4.184= -3694.035180.16 4.184= -2781.8626KJ/mol Moreover, we can calculate the standard enthalpy of combustion of glucose, the used formula:

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Hcombustion= (product)v Hf0- (reactants) v Hi0 Where v is the stochiometric coefficient of the reaction And using the following given informations: Hf0( H2O)=-285.83KJ/mol Hf0(CO2)= -393.509KJ/mol Thus, Hf0(glucose)=6 Hf0( H2O)+ 6 Hf0(CO2)- 6 Hf0(O2)- Hcombustion = -648.394 KJ/mol.

Sample #10: Doing the same calculations for sample 10 we get:

Total mass 0.0001 g % glucose 0.8 % % benzoic acid 1% M glucose M benzoic acid U glucose Table 6: sample 10 Uglucose=(1/ mglucose) (-CvT - mUbenzoic acid-mfuseUfuse-meqU(N2) ) =(1/0.6641)(2422.905*1.84897- 0.2846*-6318 0.0129*-1400 4.40*0.0709*14.1)=-4017.6396cal/g -4017.6396cal/g 0.9487 70.00% 30.00% 0.6641 g 0.2846g

Uglucose( for sample 10) = -4017.6396cal/g

Then, Hcombustion=Uglucose=-4017.6396cal/g Hm(76)= H M 4.184= -4017.6396cal/g 180.16 4.184= -3028.454 KJ/mol Next, the standard enthalpy of combustion of glucose is calculated:
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Hf0(glucose)=6 Hf0( H2O)+ 6 Hf0(CO2)- 6 Hf0(O2)- Hcombustion = -568.667 KJ/mol

The average value of Hm and Hf0 of glucose:

The average value of enthalpy of combustion: Hm= -3855.854 KJ/mol The average value of standard enthalpy of combustion of glucose: Hf0= -609.1805 KJ/mol.

Sample #11 (unknown):

Mass of the unknown=0.6979g Mass of benzoic acid= 0.2957 g Mass of pellet= 0.9656 g % unknown = (0.6979/ (0.6979+0.2957))*100=70.24% %benzoic acid = (0.2957/ (0.6979+0.2957))*100=29.76%

mass of benzoic acid in the pellet = 0.965629.76%= 0.2873g mass of unknown in the pellet= 0.6782g Uunknown =(1/ munknown) (-CvT - mUbenzoic acid-mfuseUfuse-meqU(N2) ) = -3656.628 cal/g Uunkown( for unknown sample) = -3656.628 cal/g Total mass 0.0001 g % glucose 0.8 % % benzoic acid 1% 0.9656 70.24% 29.76%

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M glucose M benzoic acid U glucose Table 7:sample 11 (unknown)

0.6782 g 0.2873 g -3656.628cal/g

Discussion:
Comparison to literature value
A constant volume oxygen bomb calorimeter was used for the determinantion of the enthalpy of combustion of glucose of an unknown sugar.
| | | |

Function Hcombustion Hoformation

Experimental

Theoretical [1]

% error 13.45% 29.79%

-3855.854 -609.1805

-3508.00 -1068.04

Table 8: experimental and theoretical values

There are errors obtained in our result due to many factors: The titration of nitric acid where the added volume of Na2CO3 could hold an error in addition from the burette and an error in reading the value obtained, where the change in color of the methyl orange as indicator from orange to yellow is hard to be noticed directly which might contribute to an excess addition of Na2CO3. 2. Errors due to the uncertainty of instruments used like the analytical balance (0.0001 g) and thermostat uncertainty ((0.000010C), where we might also encounter reading errors. 3. The fact that we neglect the pressure effect on the values of energy and enthalpy, where in reality the effect of pressure changing on the energy and enthalpy is very
1.

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small relative to the accompanied chemical changes, which causes a certain error(2). 4. Another value neglected was the contribution of Water and carbon dioxide on the heat of combustion because we used the same Cv for calculations for benzoic acid and for glucose and the unknown sugar. 5. Still there would be certain errors encountered that would affect our readings and values. 6. Other problems may occur in transferring material and various substance from a place to another or from a vessel to another which may lead to some loss of our substance.

Aerobic and Anaerobic Respiration:(3)

Aerobic respiration is the process in which glucose is converted into CO2 and H2O in the presence of oxygen, releasing large amounts of ATP (3). The process of an aerobic respiration is represented in this equation: Glucose + Oxygen Energy + Carbon dioxide + Water During the process of aerobic respiration 38 molecules of ATP are produced for every molecule of glucose that is utilized (3). Anaerobic respiration is the cellular respiration which takes place in the absence of oxygen. The process of anaerobic respiration is relatively less energy yielding as compared to the aerobic respiration process. The process of anaerobic respiration for production of energy can occur in either of the ways represented below : Glucose Energy (ATP) + Ethanol + Carbon dioxide Glucose Energy (ATP) + Lactic acid The enthalpy of the combustion of glucose is -2808.00KJ/mol via aerobic respiration while the enthalpy of combustion of anaerobic fermentation is -1344.00KJ/mol then the total will be 2688.00KJ/mol. The difference between the aerobic respiration and anaerobic fermentation is around 120KJ/mol.

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Calculation of the strain energy of cyclopropane:

Strain energy is the energy associated with every compound, corresponding to the bending or stretching of bond from their normal state as a result of geometric requirement. (4)

The standard enthalpy difference of the dissociation of cyclopropane is only as a function of strain energy S. The standard enthalpy of dissociation Hdis is the sum of the bond energies B. B values are positive and for stable compounds, Hdis is positive 3. Hdis= Bi-S+R; Bi is the bond energy, S strain energy, R is resonance energy, result from aromatic character. Cyclohexane carboxylate has a lower strain energy than n-butyl cyclopropane because the angle of cyclohexane is around 1090 while n-butylcyclopropane is approximately 600. Bomb calorimetry experiment is done for the two compounds so Hcombustion will be measured and the strain energy can be deduced. In this case the strain energy of the cyclopropane is 112.887KJ/mol (4).
O
O

OCH2CH2CH2CH2

OCH3

cyclopropanecarboxylic acid

cyclohexanecarboxylic acid

Resonance energy of benzene:

The resonance energy of a compound is a measure of the extra stability of the conjugated system compared to the corresponding number of isolated double bonds (5).

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In order to identify the resonance energy of benzene a comparaison must be done between its enthalpy of combustion and that of its conjugated system. Benzene has two resonance structures. its stabilization energy(resonance energy) is determined by the bomb calorimetry. we consider the energy change for the following reaction as the resonance energy: B * (g) B (g) [5]

B* represents the Kekule form of benzene (cyclohexatriene, not resonance stabilized) and B represents the actual benzene (resonance stabilized). The combustion of Kekule benzene and actual benzene, the difference in the combustion energies corresponds to the resonance energy: Uresonance = UcombB *( g ) - UcombB ( g )
[5]

We need to combust a molecule that has similar structure as a Kekule benzene structure (i.e. something with 3 C=C, 3 C-C, and 6 C-H bonds), in condition that the molecule does not have any contributions to its internal energy (such as steric strain). We use a combination of molecules that are combined equal to a Kekule benzene structure (there is no one molecules equal to Kekule structure): TTCC 3 C=C 9 CC 18 CH where: TTCC = 1,5,9-trans,trans,cis-cyclododecatriene and CHX = cyclohexane, both strainfree. Accordingly, UcombB* ( g ) = UcombTTCC ( g ) - UcombCHX ( g ) 6 CC 12 CH 6 CH CHX 0 C=C 3 CC B* 3 C=C

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The enthalpy:

H =U + (PV ) = U +RTngas

the reaction of combustion of benzene: C6H6 (g) +15/2O2 (g) 6 CO2 (g) + 3 H2O (g) that ngas= (9-17/2) = 1/2. Substituting U=H-RTngas into Uresonance = (HcombB *( g) - 1/2RT)- (HcombB ( g )- 1/2RT)

Uresonance = HcombB *( g ) - HcombB ( g )

where: HcombB *( g ) = HcombTTCC ( g ) - HcombCHX ( g ) [3] Uresonance = HcombTTCC ( g ) - HcombCHX ( g ) - HcombB ( g ) This equation gives the resonance energy of Benzene (3).

Conclusion:
To accomplish this experiment, we used a constant volume bomb calorimeter, to measure the heat of combustion of glucose. In order to calculate the energy change associated with the combustion of glucose we observe and calculate the temperature change. Thus we will be able to calculate and determine the enthalpy of combustion and the enthalpy of formation of glucose using some thermodynamic functions. We standardize the calorimeter two times by the use of a benzoic acid of known heat of combustion, and thus we can obtain Cv of the bomb. We apply the necessary calculations to determine the relative enthalpies of glucose and of the unknown sugar (ID#78). Our results contain an error which is 13.45 % and 29.79% for enthalpy of combustion and formation relatively. This error is due to many factors explained above.

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References:
1- Bomb Calorimetry Handout.Dr. Halaoui (spring 2013)

2- Wikipedia: http://en.wikipedia.org/wiki/Benzene

3- http://www.chemistryguide.org/

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