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Pretend that you live in the 19th century and don't know the value of Avogadro's number* (or of Boltzmann's constant or of the mass or size of any molecule). Show how you could make a rough estimate of Avogadro's number from a measurement of the thermal conductivity of gas, together with other measurements that are relatively easy.

Short Answer

Expert verified

Estimating the value of Avogadro's number ,

which is,

NA≈RTPCV2kt33MV32

Step by step solution

01

To Find ℓ.

The thermal conductivity and other macroscopic properties measured for an ideal gas can be used to generate a rough estimate of Avogadro's number. The formula for thermal conductivity is:

kt=CV2Vℓv¯ Let be equation (1)

Assume we've configured the system so that we have a volume box Vand cross-sectional area A. We know that the average speed v¯is approximately the RMS speed, which is:

v¯≈vrms=3kTm

multiply with NN, so:

Let the following be Equation (2)

localid="1650414641595" v¯=3NkTNm=3NkTM=3PVM

where  Mis the total mass of the gas. Substitute from (2) into (1), so:

localid="1650414665465" kt=CV2Vℓv¯=CV2Vℓ3PVM=CV2ℓ3PMV

â„“=2CVktMV3P

02

To find N

Schroeder's expression for â„“is based on the idea that the mean path length is equal to the length of a cylinder of radius equal to the diameter and volume of the molecule equal to the average volume per molecule VN, so that:

â„“=14Ï€r2NV

where rthe radius of the molecule, To get Nfrom this formula, we need to know r, but this is a microscopic quantity that we're assuming we don't know. I can't see any way of progressing from here unless we take a different value localid="1650296672007" â„“. Since we're after only a rough approximation of Avogadro's number, we can take â„“Instead of the average distance between collisions, it should be the average distance between molecules. That is to say:

Let be equation (4)

ℓ≈VN13

We can now combine equations (4) and (3), so:

VN13=2CVktMV3P

apply the power 3on both sides:

VN≈2CVkt3MV3P32

solve for N, so:

NV≈CV2kt33PMV32→N≈CV2kt33PMV32V

N≈CV2kt33PM321V let be equation (5)

03

To find the Avogadro's number

Assuming we know the gas constant R, The ideal gas law can be used to calculate the number of moles:

n=PVRT

And Avogadro number is given by:

NA=Nn=RTPVN

substitute from equation (5) so Avogadro's number is roughly:

NA≈RTPVCV2kt33PM321V

NA≈RTPCV2kt33MV32

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Most popular questions from this chapter

When the temperature of liquid mercury increases by one degree Celsius (or one kelvin), its volume increases by one part in 550,000 . The fractional increase in volume per unit change in temperature (when the pressure is held fixed) is called the thermal expansion coefficient, β :
β≡ΔV/VΔT
(where V is volume, T is temperature, and Δ signifies a change, which in this case should really be infinitesimal if β is to be well defined). So for mercury, β =1 / 550,000 K-1=1.81 x 10-4 K-1. (The exact value varies with temperature, but between 0oC and 200oC the variation is less than 1 %.)
(a) Get a mercury thermometer, estimate the size of the bulb at the bottom, and then estimate what the inside diameter of the tube has to be in order for the thermometer to work as required. Assume that the thermal expansion of the glass is negligible.
(b) The thermal expansion coefficient of water varies significantly with temperature: It is 7.5 x 10 -4 K-1 at 100oC, but decreases as the temperature is lowered until it becomes zero at 4oC. Below 4oC it is slightly negative, reaching a value of -0.68 x 10-4K-1 at 0oC. (This behavior is related to the fact that ice is less dense than water.) With this behavior in mind, imagine the process of a lake freezing over, and discuss in some detail how this process would be different if the thermal expansion coefficient of water were always positive.


Measured heat capacities of solids and liquids are almost always at constant pressure, not constant volume. To see why, estimate the pressure needed to keep Vfixed as Tincreases, as follows.

(a) First imagine slightly increasing the temperature of a material at constant pressure. Write the change in volume,dV1, in terms of dTand the thermal expansion coefficient βintroduced in Problem 1.7.

(b) Now imagine slightly compressing the material, holding its temperature fixed. Write the change in volume for this process, dV2, in terms of dPand the isothermal compressibility κT, defined as

κT≡−1V∂V∂PT

(c) Finally, imagine that you compress the material just enough in part (b) to offset the expansion in part (a). Then the ratio of dPtodTis equal to (∂P/∂T)V, since there is no net change in volume. Express this partial derivative in terms of βandκT. Then express it more abstractly in terms of the partial derivatives used to define βandκT. For the second expression you should obtain

∂P∂TV=−(∂V/∂T)P(∂V/∂P)T

This result is actually a purely mathematical relation, true for any three quantities that are related in such a way that any two determine the third.

(d) Compute β,κT,and(∂P/∂T)Vfor an ideal gas, and check that the three expressions satisfy the identity you found in part (c).

(e) For water at 25∘C,β=2.57×10−4K−1andκT=4.52×10−10Pa−1. Suppose you increase the temperature of some water from 20∘Cto30∘C. How much pressure must you apply to prevent it from expanding? Repeat the calculation for mercury, for which (at25∘C)β=1.81×10−4K−1andκT=4.04×10−11Pa−1

Given the choice, would you rather measure the heat capacities of these substances at constant vor at constant p?

Suppose you open a bottle of perfume at one end of a room. Very roughly, how much time would pass before a person at the other end of the room could smell the perfume, if diffusion were the only transport mechanism? Do you think diffusion is the dominant transport mechanism in this situation?

A frying pan is quickly heated on the stovetop 200∘CIt has an iron handle that is 20cmlong. Estimate how much time should pass before the end of the handle is too hot to grab with your bare hand. (Hint: The cross-sectional area of the handle doesn't matter. The density of iron is about7.9g/cm3and its specific heat is 0.45J/g⋅∘C).

Calculate the total thermal energy in a liter of helium at room temperature and atmospheric pressure. Then repeat the calculation for a liter of air.

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