Topic 3 of 5
Use the ideal-gas equation
An ideal-gas state is described by absolute pressure, gas volume, particle number and thermodynamic temperature. Convert the units and name the fixed quantities before comparing two states.
Use one consistent set of quantities
Use p in Pa, V in m3 and T in K. N is the number of gas particles; n is the amount in mol, with N = nNA and Nk = nR. For a molecular gas, N counts molecules.
The units agree: Pa m3 = N m = J, where N here is the newton unit. On the particle side, a dimensionless count multiplied by J/K and K also gives J. This is a relation between equilibrium state quantities; pV is not automatically the energy transferred by heating during a process.
Estimate the pressure scale
For roughly half a mole near room temperature, use T of order 300 K, R of order 8 J/(mol K) and V of order 10-2 m3. Then nRT/V is of order 105 Pa. These rough supplied scales help catch a volume conversion error before precise substitution.
Worked gas state
0.500 mol in 12.0 litres
The supplied gas has Celsius temperature 26.85°C. Convert both temperature and volume:
V = 12.0 × 10-3 = 0.0120 m3
p = nRT/V
= [0.500(8.31)(300)]/0.0120
= 103875 Pa ≈ 1.04 × 105 Pa
Using N = 3.01 × 1023 and k = 1.38 × 10-23 J/K instead gives 103845 Pa, the same three-significant-figure result. The small difference arises from the supplied constants being rounded separately.
For volume conversions, 1 litre = 10-3 m3 and 1 cm3 = 10-6 m3. Leaving 12.0 litres as 12.0 m3 makes the pressure a thousand times too small.
Optional check An ideal gas has amount 0.500 mol, volume 12.0 litres and Celsius temperature 26.85 degrees C. With R = 8.31 J/(mol K), what is its absolute pressure?
Use absolute pressure and number density
Gauge pressure is a pressure difference relative to the ambient pressure. A sensor reading 20 kPa above a supplied ambient pressure of 100 kPa gives an absolute gas pressure of 120 kPa. Zero gauge pressure means equality with ambient pressure, not zero absolute pressure or no particles.
1 atm = 101325 Pa
1.20 atm = 121590 Pa ≈ 1.22 × 105 Pa
The standard atmosphere is a defined pressure unit. The actual local atmospheric pressure need not equal 1 atm.
Number density is particle count per unit volume, N/V, in m-3. For the 0.500 mol sample above:
≈ 2.51 × 1025 m-3
p = (N/V)kT
Here n means amount in mol. In another context, n may denote number density instead. Check the quantity and unit rather than assuming the letter always has the same meaning.
Derive controlled comparisons
For a fixed number of particles, pV/T = Nk is constant. Hence p1V1/T1 = p2V2/T2. Holding one further quantity fixed gives:
| Also fixed | Result | Graph |
|---|---|---|
| Temperature T | pV constant; p ∝ 1/V | p against V is a reciprocal curve |
| Volume V | p/T constant; p ∝ T | p against T is a line through the kelvin origin |
| Pressure p | V/T constant; V ∝ T | V against T is a line through the kelvin origin |
Name the fixed quantities before comparing states
These two ideal-model comparisons use the 0.500 mol sample, with the same fixed particle number N. They are separate controlled changes from its 300 K, 12.0 litre, 103.875 kPa state.
Fixed N and T = 300 K: reciprocal pressure-volume curve
A: 6.0 litres, 207.75 kPa. B: 12.0 litres, 103.875 kPa. C: 24.0 litres, 51.9375 kPa. Here 1 kPa litre = 1 J, so all three products pV equal 1246.5 J.
Fixed N and p = 103875 Pa: volume follows kelvin temperature
A: 300 K, 12.0 litres. B: 360 K, 14.4 litres. The dashed part is an ideal-model extrapolation; a real gas need not remain a gas or remain ideal at much lower temperatures.
For that sample, warming from 300 to 360 K at constant pressure gives V2 = 12.0(360/300) = 14.4 litres. If volume is held fixed instead, p2 = 103875(360/300) = 124650 Pa, or about 1.25 × 105 Pa. These are two different changes from the same starting state.
A leaking container does not keep N fixed. A graph against Celsius temperature does not pass through its zero-temperature origin. State the controls and scale whenever claiming proportionality.
Investigate pressure at fixed volume
A sealed rigid vessel in a controlled water bath can be connected to an absolute-pressure sensor. Vary the bath temperature in steps and record settled gas pressure and temperature, aiming to keep the amount and total gas volume fixed.
Choose suitable instrument ranges and record pressure and thermometer resolutions. Check the sensor's zero or pressure reference, check for leaks and use a temperature range that gives clearly resolvable pressure changes. Allow time for the gas to settle after each change.
The gas in the connecting tube is part of the system too. Include its volume and arrange for the gas to be approximately at one temperature; a large tube volume left at room temperature complicates the comparison. The bath thermometer does not prove that the gas has already reached that temperature.
Read a separate generated data example
The following values describe a different model sample, whose pressure is 100.000 kPa at 300 K. They do not describe the 103.875 kPa starting state above. They are generated from p/T = 100000/300 Pa/K and rounded to 0.001 kPa; the displayed digits do not claim an instrument's resolution.
| T / K | p / kPa |
|---|---|
| 300 | 100.000 |
| 320 | 106.667 |
| 340 | 113.333 |
| 360 | 120.000 |
Measure one gas system after its temperature settles
The graphs below use a separate fixed-N, fixed-V model sample: its pressure is 100.000 kPa at 300 K. It is not the 103.875 kPa sample in the preceding comparison.
A sealed rigid vessel in a controlled bath
A bath reading is usable as the gas temperature only after suitable thermal equilibrium. Keep N and the effective gas volume fixed, measure absolute pressure, and account for leaks and connecting-tube volume.
Absolute pressure against kelvin temperature
Solid line and filled points: the supplied 300-360 K range. Dashed line: ideal-model extrapolation. The generating ratio is p/T = 333.333... Pa/K.
The same model against Celsius temperature
Solid line and filled points: the supplied 300-360 K range. Dashed line: ideal-model extrapolation. The brown reference is 0 °C, not zero kelvin. The model's zero-pressure intercept is -273.15 °C.
These pressures were generated from an ideal relation and rounded to 0.001 kPa. Those digits do not specify an instrument's resolution. A real gas can condense or depart from the ideal model before an extrapolated zero is approached.
The unrounded generating model has p/T = 333.333... Pa/K. Its kelvin graph passes through zero. On a Celsius horizontal axis, the same model instead has p = 91.05 kPa at 0°C and extrapolates to zero pressure at -273.15°C.
Only the supplied range is represented by the data. A line fitted there does not establish that a real gas stays ideal down to 0 K: changes such as condensation invalidate that extension.
Optional spreadsheet application
Find a pressure-temperature gradient
Use the four generated pairs above. The Motion spreadsheet method explains manual entry, copying formulas and numeric scatter graphs.
- Put
temperature / Kin A1 andpressure / kPain B1. Enter the four pairs in A2:B5 as numbers. - Use C1 for
absolute pressure / Paand D1 forpressure / temperature / Pa K^-1. Enter=B2*1000in C2 and=C2/A2in D2. Fill both formulas through row 5 only. - Create a numeric XY scatter graph with A2:A5 horizontally and C2:C5 vertically. Label the axes T / K and p / Pa. Fit a straight line with a free intercept and display its equation; do not force it through zero before examining the result.
- Interpret the gradient using p = (N/V)kT. Divide its value in Pa/K by k = 1.38 × 10-23 J/K to estimate N/V. Change displayed precision without rounding away stored values.
Compare the fitted model
The ratios in column D are close to 333.333 Pa/K. The rounded data give a free-intercept fit with gradient 333.330 Pa/K and intercept +1.10 Pa.
= 333.330/(1.38 × 10-23)
≈ 2.42 × 1025 m-3
The unrounded generating model has zero intercept and gradient 333.333... Pa/K. These small fitted departures arise from rounding, not experimental scatter. They do not provide new experimental evidence for the model.
Explain a practical departure causally
- Reading too early during warming: gas still below the recorded bath temperature has lower pressure than the equilibrium prediction at that bath temperature. Repeating the same rushed procedure does not remove this bias.
- Leakage: the particle number changes, so successive points no longer test the same fixed-N relationship.
- Uncorrected gauge readings: a constant atmospheric offset changes the intercept and p/T. It need not change the slope of a pressure-temperature line.
- Vessel expansion: volume may change slightly as temperature rises, weakening the assumed fixed-volume control.
For real readings, retain instrument precision and uncertainties and compare the measured gradient and intercept with the stated model before claiming agreement. An area under a pressure-temperature graph is not heat supplied: its units are not joules.