Why is this calculation of the enthelpy of combustion wrong?

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Homework Help Overview

The discussion revolves around the calculation of the enthalpy of combustion for a sample of octane (C8H18) burned in a bomb calorimeter. Participants are examining the heat transferred to the calorimeter and the implications of the signs used in the calculations.

Discussion Character

  • Mixed

Approaches and Questions Raised

  • The original poster attempts to calculate the heat transferred using the calorimeter's heat capacity and temperature change, leading to confusion about the signs of enthalpy changes in exothermic reactions.
  • Some participants question the interpretation of heat transfer signs and the definition of heat of combustion as it relates to the number of moles.
  • Others suggest clarifying the distinction between heat transferred to the calorimeter and the reaction mixture.

Discussion Status

Participants are exploring different interpretations of the signs in the calculations and discussing the correct approach to determining the heat of combustion per mole. There is acknowledgment of the original poster's confusion regarding the positive and negative signs associated with enthalpy changes.

Contextual Notes

There is an ongoing discussion about the conventions used in thermodynamics, particularly regarding exothermic reactions and the calculation of enthalpy changes. The original poster expresses uncertainty about the reasoning behind certain steps in the calculation.

Buffu
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Homework Statement


A 1.250 g sample of ##C_8H_18## is burnt with excess oxygen in a bomb calorimeter. Change in temperature is from 294.05 K to 300.78 K. If heat capacity of the calorimeter is 8.93 kJ/K. Find the heat transferred to the calorimeter. Also calculate the enthalpy of combustion of the sample of octane.

Homework Equations


##q_v = \triangle U = C \times \triangle T##
##\triangle H = \triangle U + \triangle n_{(g)}RT##
##C_8H_{18} (s) + {25\over 2}O_2 \longrightarrow 8CO_2(g) + 9H_2O(l)##

The Attempt at a Solution


I use the first equation to find ##q_{transferred}= (300.78 - 294.05) \times 8.93 J = 60.1 kJ##
Since combustion is exothermic, Thus ##q_{transferred} = 60.1 kJ##.

Since this reaction is carried the volume is constant but pressure isn't.

Since ##-q_{transferred} = \triangle U = -60.1 kJ##
Now enthalpy of combustion is ##\triangle H = \triangle U + \triangle n_{(g)}RT##

##\triangle n_{(g)} = (8 - 12.5) \times {1.25 \over 114}##

Since ##-q_{transferred} = \triangle U = -60.1 J## for exothermic reactions

##\therefore \triangle H = -60.1 + 8.314 \times 294.05 \times (8 - 12.5) \times {1.25 \over 114} \times 10^{-3}##
Which i got from calculator as ##-60.221 kJ##.

Now my second answer is incorrect.

In the solution ##\triangle U## is taken positive and ##\triangle_{combustion} H = {\triangle U \over \text{number of moles}}##

I don't understand the reasoning behind taking ##\triangle U## positive as combustion is exothermic and thus heat is evolved, which by convention means that we need to get -ve sign in the answer.
For ##\triangle H## calculation by the author, I don't even have a clue how they did that.
 
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Did you say that you got the heat transferred to the calorimeter correct?
 
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Chestermiller said:
Did you say that you got the heat transferred to the calorimeter correct?

Yes as per the book. I think it should be -ve but, I am not sure.
 
Buffu said:
Yes as per the book. I think it should be -ve but, I am not sure.
Well, the heat transferred to the calorimeter is positive. The heat transferred to the reaction mixture is negative.

You correctly determined the change in enthalpy of the reaction mixture in the experiment. But, the heat of combustion, is defined as the change in enthalpy per mole. So you need to divide by the number of moles to get the heat of combustion. And, your interpretations regarding sign of the heat of combustion as minus the enthalpy change are correct.
 
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Chestermiller said:
Well, the heat transferred to the calorimeter is positive. The heat transferred to the reaction mixture is negative.

You correctly determined the change in enthalpy of the reaction mixture in the experiment. But, the heat of combustion, is defined as the change in enthalpy per mole. So you need to divide by the number of moles to get the heat of combustion. And, your interpretations regarding sign of the heat of combustion as minus the enthalpy change are correct.

So all I need to do is ##-60.221\over ({1.25 \over 114})## to get the correct answer.
Thank you very much.
 

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