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Avogadro’s law

Previously in Chemistry one has learned about Avogadro’s hypothesis:

Equal volumes of any gas, at the same temperature and pressure, contain the same number of molecules.

Avogardo's Hypothesis gas

Reasoning 

(from Modern Chemistry, Davis, HRW)

In 1811, Avogadro found a way to explain Gay-Lussac’s simple ratios of combining volumes without violating Dalton’s idea of indivisible atoms. He did this by rejecting Dalton’s idea that reactant elements are always in monatomic form when they combine to form products. He reasoned that these molecules could contain more than one atom.

Avogadro also put forth an idea known today as Avogadro’s law: equal volumes of gases at the same temperature and pressure contain equal numbers of molecules.

It follows that at the same temperature and pressure, the volume of any given gas varies directly with the number of molecules.

Avogadro’s law also indicates that gas volume is directly proportional to the amount of gas, at a given temperature and pressure.

Note the equation for this relationship.

   V = kn

Here, n is the amount of gas, in moles, and k is a constant.

Avogadro’s reasoning applies to the combining volumes for the reaction of hydrogen and oxygen to form water vapor.

Dalton had guessed that the formula of water was HO, because this formula seemed to be the most likely formula for such a common compound.

But Avogadro’s reasoning established that water must contain twice as many H atoms as O atoms, consistent with the formula H2O.

As shown below, the coefficients in a chemical reaction involving gases indicate the relative numbers of molecules, the relative numbers of moles, and the relative volumes.

Avogadro gas reaction

The simplest hypothetical formula for oxygen indicated 2 oxygen atoms, which turns out to be correct. The simplest possible molecule of water indicated 2 hydrogen atoms and 1 oxygen atom per molecule, which is also correct.

Experiments eventually showed that all elements that are gases near room temperature, except the noble gases, normally exist as diatomic molecules.

As an equation

Avogadro’s Law – also known as Avogadro–Ampère law

when temperature and pressure are held constant:

volume of a gas is directly proportional to the # moles (or # particles) of gas

n1 / V1 = n2 / V2

or

Avogadro's Law gas

What does this imply?

As # of moles of gas increases, the volume of the gas also increases.

As # of moles of gas is decreased, the volume also decreases.

Thus, # of molecules (or atoms) in a specific volume of ideal gas is independent of their size (or molar mass) of the gas.

Important! This is not a law of physics! 

Rather, this is a generally useful rule, which is only valid when gas temperature and pressure is low enough for the atoms to usually be far apart from each other.  As we begin to deal with more extreme cases, this rule doesn’t hold up.

At what point does Avogadro’s law not apply?

Example problems

These problems are from The Chem Team, Kinetic Molecular Theory and Gas Laws

Example #1: 5.00 L of a gas is known to contain 0.965 mol. If the amount of gas is increased to 1.80 mol, what new volume will result (at an unchanged temperature and pressure)?

Solution:

I’ll use V1n2 = V2n1

(5.00 L) (1.80 mol) = (x) (0.965 mol)

x = 9.33 L (to three sig figs)


Example #2: A cylinder with a movable piston contains 2.00 g of helium, He, at room temperature. More helium was added to the cylinder and the volume was adjusted so that the gas pressure remained the same. How many grams of helium were added to the cylinder if the volume was changed from 2.00 L to 2.70 L? (The temperature was held constant.)

Solution:

1) Convert grams of He to moles:

2.00 g / 4.00 g/mol = 0.500 mol

2) Use Avogadro’s Law:

V1 / n1 = V2 / n2

2.00 L / 0.500 mol = 2.70 L / x

x = 0.675 mol

3) Compute grams of He added:

0.675 mol – 0.500 mol = 0.175 mol

0.175 mol x 4.00 g/mol = 0.7 grams of He added


Example #3: A balloon contains a certain mass of neon gas. The temperature is kept constant, and the same mass of argon gas is added to the balloon. What happens?

(a) The balloon doubles in volume.
(b) The volume of the balloon expands by more than two times.
(c) The volume of the balloon expands by less than two times.
(d) The balloon stays the same size but the pressure increases.
(e) None of the above.

Solution:

We can perform a calculation using Avogadro’s Law:

V1 / n1 = V2 / n2

Let’s assign V1 to be 1 L and V2 will be our unknown.

Let us assign 1 mole for the amount of neon gas and assign it to be n1.

The mass of argon now added is exactly equal to the neon, but argon has a higher gram-atomic weight (molar mass) than neon. Therefore less than 1 mole of Ar will be added. Let us use 1.5 mol for the total moles in the balloon (which will be n2) after the Ar is added. (I picked 1.5 because neon weighs about 20 g/mol and argon weighs about 40 g/mol.)

1 / 1 = x / 1.5

x = 1.5

answer choice (c).


Example #4: A flexible container at an initial volume of 5.120 L contains 8.500 mol of gas. More gas is then added to the container until it reaches a final volume of 18.10 L. Assuming the pressure and temperature of the gas remain constant, calculate the number of moles of gas added to the container.

Solution:

V1 / n1 = V2 / n2

5.120 L 18.10 L
–––––––– = ––––––
8.500 mol x

x = 30.05 mol <— total moles, not the moles added

30.05 – 8.500 = 21.55 mol (to four sig figs)

Notice the specification in the problem to determine moles of gas added. The Avogadro Law calculation gives you the total moles required for that volume, NOT the moles of gas added. That’s why the subtraction is there.

.

Charles’s Law

Charles’s Law – also known as Charles and Gay-Lussac’s Law.

Describes how gases tend to expand when heated.

When the pressure on a sample of a dry gas is held constant, the temperature and the volume will be in direct proportion.

Volume proportional to temperature

(Only true when measuring temperature on an absolute scale)

This relationship can be written as:

Charles's law gas

-> Gas expands as the temperature increases

-> Gas contracts as the temperature decreases

This relationship can be written as:

Charles's law gas alternate

Important! This is not a law of physics! Rather, this is a generally useful rule, which is only valid when gas temperature and pressure is low enough for the atoms to usually be far apart from each other.  As we begin to deal with more extreme cases, this rule doesn’t hold up.

Let’s see this in action!

Origin

Named after Jacques Alexandre César Charles (1746 – 1823)  a French inventor, scientist, mathematician, and balloonist. Just so we’re all clear on this, he was kind of a mad scientist. And I say that with the utmost approval!

first balloon flight by Charles and Robert 1783

Contemporary illustration of the first flight by Prof. Jacques Charles with Nicolas-Louis Robert, December 1, 1783. Viewed from the Place de la Concorde to the Tuileries Palace (destroyed in 1871)

 

.Apps

Charles’s law app

Learning standards

Massachusetts Science and Technology/Engineering Curriculum Framework

8.MS-PS1-4. Develop a model that describes and predicts changes in particle motion, relative spatial arrangement, temperature, and state of a pure substance when thermal energy is added or removed.

Next Generation Science Standards

MS-PS1-4. Develop a model that predicts and describes changes in particle motion, temperature, and state of a pure substance when thermal energy is added or removed.

College Board Standards

Objective C.1.5 States of Matter

C-PE.1.5.2 Explain why gases expand to fill a container of any size, while liquids flow and spread out to fill the bottom of a container and solids hold their own shape. Justification includes a discussion of particle motion and the attractions between the particles.

C-PE.1.5.3 Investigate the behavior of gases. Investigation is performed in terms of volume (V ), pressure (P ), temperature (T ) and amount of gas (n) by using the ideal gas law both conceptually and mathematically.

Common Core Math

Analyze proportional relationships and use them to solve real-world and mathematical problems.

Ratios & Proportional Relationships

Ratios & Proportional Relationships

CCSS.MATH.CONTENT.7.RP.A.2

Recognize and represent proportional relationships between quantities.

CCSS.MATH.CONTENT.7.RP.A.2.A

Decide whether two quantities are in a proportional relationship, e.g., by testing for equivalent ratios in a table or graphing on a coordinate plane and observing whether the graph is a straight line through the origin.

CCSS.MATH.CONTENT.7.RP.A.2.B

Identify the constant of proportionality (unit rate) in tables, graphs, equations, diagrams, and verbal descriptions of proportional relationships.

Boyle’s law (gas laws)

A general relationship between pressure and volume: Boyle’s Law

As the pressure on a gas increases, the volume of the gas decreases because the gas particles are forced closer together.

Conversely, as the pressure on a gas decreases, the gas volume increases because the gas particles can now move farther apart.

Example: Weather balloons get larger as they rise through the atmosphere to regions of lower pressure because the volume of the gas has increased; that is, the atmospheric gas exerts less pressure on the surface of the balloon, so the interior gas expands until the internal and external pressures are equal.

from Libretexts, Chemistry, 5.3: The Simple Gas Laws: Boyle’s Law, Charles’s Law and Avogadro’s Law, CC BY-NC-SA 3.0.

This means that, at constant temperature, the pressure (P) of a gas is inversely proportional to the volume (V).

PV = c

Important! This is not a law of physics! Rather, this is a generally useful rule, which is only valid when gas temperature and pressure is low enough for the atoms to usually be far apart from each other.  As we begin to deal with more extreme cases, this rule doesn’t hold up.

Let’s see the relationship in action, here:

Boyle's law pressure temp

from http://www.grc.nasa.gov/WWW/K-12/airplane/boyle.html

How was this general rule discovered?

Early scientists explored the relationships among the pressure of a gas (P) and its temperature (T), volume (V), and amount (n) by holding two of the four variables constant (amount and temperature, for example), varying a third (such as pressure), and measuring the effect of the change on the fourth (in this case, volume).

The history of their discoveries provides several excellent examples of the scientific method.

The Irish chemist Robert Boyle (1627–1691) carried out some of the earliest experiments that determined the quantitative relationship between the pressure and the volume of a gas. Boyle used a J-shaped tube partially filled with mercury.

In these experiments, a small amount of a gas or air is trapped above the mercury column, and its volume is measured at atmospheric pressure and constant temperature. More mercury is then poured into the open arm to increase the pressure on the gas sample.

The pressure on the gas is atmospheric pressure plus the difference in the heights of the mercury columns, and the resulting volume is measured. This process is repeated until either there is no more room in the open arm or the volume of the gas is too small to be measured accurately.

Boyle's Law pressure temp of a gas

Details: Boyle’s Experiment Using a J-Shaped Tube to Determine the Relationship between Gas Pressure and Volume.

(a) Initially the gas is at a pressure of 1 atm = 760 mmHg (the mercury is at the same height in both the arm containing the sample and the arm open to the atmosphere); its volume is V.

(b) If enough mercury is added to the right side to give a difference in height of 760 mmHg between the two arms, the pressure of the gas is 760 mmHg (atmospheric pressure) + 760 mmHg = 1520 mmHg and the volume is V/2.

(c) If an additional 760 mmHg is added to the column on the right, the total pressure on the gas increases to 2280 mmHg, and the volume of the gas decreases to V/3

(This section from from Libretexts, Chemistry, 5.3: The Simple Gas Laws: Boyle’s Law, Charles’s Law and Avogadro’s Law, CC BY-NC-SA 3.0)

 

Learning standards

Massachusetts Science and Technology/Engineering Curriculum Framework

8.MS-PS1-4. Develop a model that describes and predicts changes in particle motion, relative spatial arrangement, temperature, and state of a pure substance when thermal energy is added or removed.

Next Generation Science Standards

MS-PS1-4. Develop a model that predicts and describes changes in particle motion, temperature, and state of a pure substance when thermal energy is added or removed.

College Board Standards

Objective C.1.5 States of Matter

C-PE.1.5.2 Explain why gases expand to fill a container of any size, while liquids flow and spread out to fill the bottom of a container and solids hold their own shape. Justification includes a discussion of particle motion and the attractions between the particles.

C-PE.1.5.3 Investigate the behavior of gases. Investigation is performed in terms of volume (V ), pressure (P ), temperature (T ) and amount of gas (n) by using the ideal gas law both conceptually and mathematically.

Common Core Math

Analyze proportional relationships and use them to solve real-world and mathematical problems.

Ratios & Proportional Relationships

Ratios & Proportional Relationships

CCSS.MATH.CONTENT.7.RP.A.2

Recognize and represent proportional relationships between quantities.

CCSS.MATH.CONTENT.7.RP.A.2.A

Decide whether two quantities are in a proportional relationship, e.g., by testing for equivalent ratios in a table or graphing on a coordinate plane and observing whether the graph is a straight line through the origin.

CCSS.MATH.CONTENT.7.RP.A.2.B

Identify the constant of proportionality (unit rate) in tables, graphs, equations, diagrams, and verbal descriptions of proportional relationships.

 

Vapor cones and mach cones

A vapor cone, also known as shock collar or shock egg, is a visible cloud of condensed water which can sometimes form around an object moving at high speed through moist air, for example an aircraft flying at transonic speeds.

FA-18 Hornet breaking sound barrier July 1999 US Navy

When the localized air pressure around the object drops, so does the air temperature. If the temperature drops below the saturation temperature a cloud forms.

prandtl glauert vapor cloud Mach
In the case of aircraft, the cloud is caused by supersonic expansion fans decreasing the air pressure, density and temperature below the dew point. Then pressure, density and temperature suddenly increase across the stern shock wave associated with a return to subsonic flow behind the aircraft. Since the local Mach number is not uniform over the aircraft, parts of the aircraft may be supersonic while others remain subsonic — a flight regime called transonic flight.


 

A vapor cone is caused by the formation of so-called ‘Prandtl–Meyer’ expansion fans, which temporarily decrease the air pressure, density and temperature below the air’s dew point. It is not the same thing as the Mach Cone (which is an invisible pressure front), but the two often occur in tandem, allowing us to pretend that we have just seen the sound barrier broken. In this incredible clip of a Boeing F/A-18 Hornet flying at a height of 25 feet, you can see both the Vapor Cone and evidence of the Mach Cone on the surface of the water…

http://physicsfootnotes.com/vapor-cone-versus-mach-cone/

 

Triple point

The following is from the Learner.Org Chemistry course https://www.learner.org/courses/chemistry/about/about.html

Once the gas laws were formulated, chemists could analyze how materials transitioned from one phase to another, and how temperature and pressure affected these changes.

In 1897, a British metallurgist named Sir William Chandler Roberts-Austen (1843–1902) produced what is widely regarded as an early form of a now-common tool in chemistry and related disciplines: the phase diagram.

Modern phase diagrams show relationships between different states of matter under various combinations of temperature and pressure.

A substance can exist in two different states at once—for example, as a liquid and a gas, with molecules cycling from one state to the other.

It is also possible for a material to be both solid and liquid, with both melting and freezing taking place at its edges, or to exist as a solid and a gas.

Phase diagrams show what forms a substance will take under given temperatures and pressure levels, and where these equilibrium lines (when equal numbers of molecules are changing form in both directions) are located. (Figure 2-11)

Figure 2-11. Generic Phase Diagram for a Single Substance © Science Media Group. https://www.learner.org/courses/chemistry/text/text.html?dis=U&num=Ym5WdElUQS9NeW89&sec=YzJWaklUQS9OeW89

Figure 2-11. Generic Phase Diagram for a Single Substance
© Science Media Group.
https://www.learner.org/courses/chemistry/text/text.html?dis=U&num=Ym5WdElUQS9NeW89&sec=YzJWaklUQS9OeW89

Amazing: See a flask of liquid cyclohexane brought to the brink of its triple-point:
suddenly it can boil and freeze at the same time.

http://physicsfootnotes.com/triple-point/

A volumetric flask containing liquid cyclohexane is depressurized to a very low pressure by a turbo-molecular vacuum pump. The rapid drop in pressure results in a rapid drop in temperature, causing the substance to temporarily freeze, but the system is unstable, flirting with the triple point (a point of pressure and temperature at which a substance is simultaneously solid, liquid, and gas). The result is a fluctuation between all three states of matter, in a spectacular display of chemistry and physics in action.

http://physicsfootnotes.com/triple-point/