Basic Thermodynamics; Change in U at Constant Pressure

AI Thread Summary
The discussion centers on calculating the change in internal energy (ΔU°) for a combustion reaction at constant pressure, where ΔH° is given as -1299.5 kJ. The user initially calculates the work done on the system, resulting in a ΔU of -61.3 kJ, which contradicts the expected value of -1298.3 kJ. The confusion arises from a dimensional analysis error, mistaking kPa·L for kJ instead of J. Ultimately, the correct understanding is that work is done on the system due to the decrease in gas volume, and the user acknowledges the mistake in unit conversion. The thread highlights the importance of careful dimensional analysis in thermodynamic calculations.
Silvius
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Homework Statement


What is the ΔU° at 25°C for the following reaction at constant pressure:

C_{2}H_{2} (g) + 5/2O_{2} (g) \rightarrow 2CO_{2} (g) + H_{2}O (g) ΔH° = -1299.5kJ

Homework Equations



ΔU = Q ± W
PV = nRT
W = PΔV

The Attempt at a Solution



Since we have constant pressure, ΔH° = Q, and since we are at standard conditions P = 1atm = 101.3kPa. Additionally T = 298K (which is given anyway). I try and find the work done on the system by finding the reduction in volume;

ΔV = ΔnRT/P

ΔV = (0.5 x 8.31 x 298)/101.3 = 12.2L

W_{on system} = 101.3kPa * 12.2L = 1238.2kJ

ΔU = -1299.5kJ + 1238.2kJ = -61.3kJ

However, the answer is -1298.3kJ.

Interestingly, this answer is what I would get if I had accidently calculated the W_{on system} was in joules and forgotten to convert - but I don't see how this can be the case - I'm dealing with kPa not Pa as my unit for pressure. Any help would be much appreciated!
 
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Silvius said:

Homework Statement


What is the ΔU° at 25°C for the following reaction at constant pressure:

C_{2}H_{2} (g) + 5/2O_{2} (g) \rightarrow 2CO_{2} (g) + H_{2}O (g) ΔH° = -1299.5kJ

Homework Equations



ΔU = Q ± W
PV = nRT
W = PΔV

The Attempt at a Solution



Since we have constant pressure, ΔH° = Q, and since we are at standard conditions P = 1atm = 101.3kPa. Additionally T = 298K (which is given anyway). I try and find the work done on the system by finding the reduction in volume;

ΔV = ΔnRT/P

ΔV = (0.5 x 8.31 x 298)/101.3 = 12.2L

W_{on system} = 101.3kPa * 12.2L = 1238.2kJ

ΔU = -1299.5kJ + 1238.2kJ = -61.3kJ

However, the answer is -1298.3kJ.

Interestingly, this answer is what I would get if I had accidently calculated the W_{on system} was in joules and forgotten to convert - but I don't see how this can be the case - I'm dealing with kPa not Pa as my unit for pressure. Any help would be much appreciated!

That is because ##E_{\mbox{int}}=Q+W## applies when work is done on the system.
 
dimension10 said:
That is because ##E_{\mbox{int}}=Q+W## applies when work is done on the system.

Work is being done on the system in this case; the pressure and temperature is constant, and so a decrease in the amount of gas results in a decrease of volume of the system. That is, the surrounding constant pressure is doing work in compressing the system.

Either way, I have found my error - it was simply an error in dimensional analysis! 1kPa * 1L = 1J, not kJ! Whoops!
 
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