van der Waals Equation Study Notes

Background

The Ideal Gas Law is valid for all gasses at sufficiently low pressure. However, as pressure on an given amount of gas increases, we observe deviations to the expected values These deviation occur because the ideal gas law assumes: • gas molecules are point-sized • that when gas molecules collide, they do so elastically -- in other words that the molecules bounce off each other without being attracted to each other. The Real life conditions: • molecules are not points, they are 3 dimensional • there are attractive forces between the gas molecules The Volume reality • Since molecules are 3 dimensional, they have length, width, height and consequently volume • The gas molecules therefore use up a certain amount of the total volume of the container they are in • The actual volume available for the gas molecules to move around in is actually less than V. • The real available volume depends on the size of the gas molecule and how many gas molecules are present The Pressure Reality • There will always be certain attractive forces between a molecule of a given gas and its neighboring molecules • The attractive forces between a molecule and its neighbors will be directed away from the direction of the force with which the molecule will be hitting the container • As a result, the molecules will hit the wall of its container with less force than if the gas were ideal • The attractive forces between real gas molecules have the effect of reducing the pressure from what we would expect if we were dealing with an ideal gas. Why? Because P = F/A, the pressure is directly proportional to the force striking an area. Since the attractive forces have the effect of decreasing the force of the molecule’s collision on the container, the pressure will likewise be decreased. Making corrections for the real world situation

• 2 constants need to be introduced into the PV=nRT equation a constant to account for the attractive forces and density of the gas that impacts the ideal pressure (the constant) a constant to account for the size of the molecules which impacts the ideal volume (the constant) Calculating the Real Pressure • The pressure reduction due to the attractive forces is equal to where is a constant for a given gas 2 • Pactual = Pideal • Pideal is the P in the gas equation PV=nRT 2 • We have to add back the pressure loss of caused by the attractive forces of the gas back to the ideal state P 2 should be substituted for the P term in = • P + Calculating the Real Volume • The total volume taken up by the molecules is where is the number of gas molecules and is a constant that depends on the gas and is a measure of the size of the molecule. • We have to subtract out the total volume of the gas molecules from the total volume of the container to get the true volume we have to work with • The actual available volume is V • V– should be substituted for the V term in = . Deriving the van der Waals equation • Plug in the substitutions we calculated to address the pressure and volume corrections: = (P + 2 2 ) (V - )= expanding out the first term will give us: (P + )(V )= (the van der Waals equation) • The constant and are called the van der Waals constants and they depend on the specific gas under consideration. .

or both to answer the problem. or info that provides you with both the and constant values.• The constant has the units of L2 • bar • mol-2 (L2 • bar/mol2) and has the units of L/mol. Look for keywords like: real. ideally. (Some question may try and trick you by not providing you with a table. And sometimes this will be exactly the correct answer to the problem. compared to. to determine whether to use the ideal gas. non-ideal. substitute the given and derived values (with their proper or new units) . the difference between. Make sure that you read the question carefully so that you know what gas formula they are looking for. You will always have to use a table to look up the values of the and constants for the specific gas you are dealing with. Convert any temperature you are given to Kelvin degrees. 3. perform any initial unit conversions 3. ideal. Solving van der Waals Problems Assuming we have enough information to solve a van der Waals problem. but the fact that they mention ideal behavior means that you need to use the ideal gas law rather than the van der Waals equation. if necessary 4. etc. Look and see if they are looking for the answer to be in a specific unit. 2. Take the van der Waals equation and manipulate it to isolate the specific term we are looking for 2. if they give you a fake gas (say Gas Q). They can give you information on a real gas (say Chlorine) and its constants. Just treat it according to what they give you. don’t freak out. you cannot solve the van der Waals equation. van der Waals equation. 5. Since you were given the van der Waal constants. but turn around and ask you how it would ideally behave. In either case. we need to 1. ideal behavior. which may require you to make before or after unit conversions. Also. or else be given them in the problem. Here are some conversion formulas: 1 J·m3/mol2 = 1 m6·Pa/mol2 = 10 L2·bar/mol2 1 dm3/mol = 1 L/mol Preparing to Solve van der Waals Problems 1. you might be tempted to solve the van der Waals equation. and the only answer that you can give is that the answer cannot be determined because you do not have sufficient info.

the numerator of the first term (2 mol)(0. .(4.17 L² atm / mol²) x (2 mol)² / (1L²) P = (46. look up the van der Waals constants for the gas (or gases) if necessary plug in all the numbers you have into the equation Perform the arithmetic to solve the equation Do any final conversions to get the answer into the final units they are looking for.94 Latm) / (0. 8. Adding the exponents for each particular unit will give L•atm as the numerator units. use P= Example: What is the pressure exerted by 2 moles of ammonia at 13◦C in a 1 L container? (use a = 4.(an² / V²) P = (2 mol) (0.15 K. T is given in oC. let’s just call it at 286 K.08206 L•atm•mol-1 •K-1)(286 K1).16.16. For example. and to use the gas laws we have to be in K degrees. the first thing we have to do is look at the units we are provided.70 atm = 34.0371 L/mol as the rounded off van der Waals constants for ammonia) ( – ) ( ) To solve this problem. so the numerator units • divided by the denominator units for the first term ends up being or just atm. Doing the same with the denominator we end up with the unit L. So we convert the 10 Celsius degrees we are given in the problem by adding 273.70 atm . but for simplicity.08206 L•atm/mol •K)(286K) / (1 L – (2 mol) x 0. We are now in good shape to work the problem: P = nRT / (V-nb) . 7.15 in order to come up with the Kelvin temperature we need to use. If volume and temperature are known and they are looking for pressure. 6.0 atm Sometimes I find it easier to deal with the cross-cancellation of units by having them all expressed in exponential form rather as a fractional part of a numerator or denominator within a fraction.0371 L/mol) . This comes out to 286.17 L2 · atm/mol2 and b = 0.70 atm P = 50.9258 L) . 1.08206 L•atm/mol •K)(286 K) can be written as : (2 mol1) (0. Look back at the question to determine the final answer you need to provide and how it should be provided.4. 5.

your answer should be: The pressure exerted on the ideal gas will be 12. and the temperature is needed.083145 L•atm/mol •K)(286K) / (1 L – (2 mol) x 0. So your response should be with respect to the ideal gas.70 atm = 34.67 atm Step 2 – Now figure out the pressure that would be exerted on an ideal gas: P = nRT/V = 2 x 0.67 atm and Pideal gas = 47. If pressure and volume are given. the first term of the equation would be PV3.67 atm = 12.89 atm less than that exerted on a real gas. use T= ( )( p + ) (V .9258 L) .17 L2 · atm/mol2 and b = 0. Compare a real gas to an ideal gas How much does the pressure exerted by 2 moles of ammonia at 13◦C in a 1 L container differ from the pressure exerted on the same amount of an ideal gas? (use a = 4. If you multiply out the equation and then get V out of the denominators. .37 atm .56 atm – 34.0371 L/mol) .17 L² atm / mol²) x (2 mol)² / (1L²) Pammonia = (47.56 Latm) / (0.89 atm Step 4 – Provide your answer to the question: Re-read the question to make sure you word your answer correctly! We are asked how much does the ideal gas differ from amonia.16. which is hard to easily solve.) You won’t often find a question where you are given P and T alone and have to find the corresponding volume in a van der Waals equation problem. so the equation is really a cubic function.16. 3.56 atm so more pressure is exerted on the ideal gas And the difference is: 47.(a n² / V²) Pammonia = (2 mol) (0.70 atm Pammonia = 51.083145 x 286 / 1 Pideal gas = 47. Although the pressure exerted on ammonia is 12.(4.2.56 atm Step 3 – Compare the two pressures: Pammonia = 34.0371 L/mol as the rounded off van der Waals constants for ammonia) Step 1 -First figure out the pressure exerted on ammonia: P = nRT / (V-nb) .89 atm more than that exerted on ammonia.

. )) ) – 2.3026 and = 1. .3026 = 6.4. One contains Methane (CH4) and the other Nitrogen (N2). the larger the constant value. Example: Two identical 1 liter tanks have 1 mole of gas in them at 100 K.3861 atm – .3026 = 8. Now calculate the pressure we would get from an ideal gas: P= P= ( ) ( ( )( . = = = = = = = 2. • For the constant. ( ) )( ) = 8.3661 and = 0.038577 ( ) – ( ) ( (( )( (. the larger the constant value. An less volume will be available for the gas with the constant value. ( . )) ( ( (( )(. Comparing two real gases If we remember what the constants relate to in terms of the physical attributes of gas molecules we can draw certain conclusions about gases based on their van der Waals constants: • For the constant.3145 ) Since Nitrogen’s pressure is closer to that of an ideal gas under the given conditions.2820 atm So there is a 0. ) ) ) – ( ( . the larger the molecule and consequently the radius of the molecule. )) ( (( . )( )) ) – ( ( )( . it acts more like an ideal gas than methane. . ) ( ) ) ( . the greater the attraction will be between the gas molecules and the smaller the force with which a molecule will hit the container walls.64811 .3661 = 7.8959 atm difference in pressure between the two tanks. ) ( – ) = 8. What will be the difference between the pressures in the two tanks? Which gas behaves closest to an ideal gas? For Methane: For Nitrogen: And.6886 – 2. )( .043067 = 0.1.

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