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Suppose you have a box of atomic hydrogen, initially at room temperature and atmospheric pressure. You then raise the temperature, keeping the volume fixed.

(a) Find an expression for the fraction of the hydrogen that is ionised as a function of temperature. (You'll have to solve a quadratic equation.) Check that your expression has the expected behaviour at very low and very high temperatures.

(b) At what temperature is exactly half of the hydrogen ionised?

(c) Would raising the initial pressure cause the temperature you found in part (b) to increase or decrease? Explain.

(d) Plot the expression you found in part (a) as a function of the dimension- less variable t = kT/I. Choose the range of t values to clearly show the interesting part of the graph.

Short Answer

Expert verified

(a) An expression for the fraction of the hydrogen that is ionised as a function temperature is x=kT2P2Ï€mekTh23/2e-I/kT1+4PkT2Ï€mekTh2-3/2eI/kT-1

(b) The temperature at which exactly half of the hydrogen is ionised is T=25800K

Step by step solution

01

Given information

A box of atomic hydrogen, initially at room temperature and atmospheric pressure. Then raise the temperature, keeping the volume fixed.

02

Explanation

The equation is given by:

PpPH=kTPe2Ï€mekTh23/2e-I/kT

Where,

Iis the ionisation energy

The ratio of partial pressures equals the ratio of ionised hydrogen to non-ionised hydrogen (pressure of protons where the proton is ionised hydrogen). Let N1be the number of ionised hydrogen and NGbe the number of hydrogen in ground state.

PpPH=NING=kTPe2Ï€mekTh23/2e-I/kT

By ideal gas law,

kTPe=VNe=1ne

Where,

neis number of density of electrons

Therefore,

NING=1ne2Ï€mekTh23/2e-I/kT(1)

Electron density in terms of number density of hydrogen atoms:

ne=NING+NIn


03

Calculations

Substitute this into (1)

NING=1nNG+NINI2Ï€mekTh23/2e-I/kTNI2NGNG+NI=1n2Ï€mekTh23/2e-I/kT(2)

Let NT be the number of ionised atoms plus the number of non ionised atoms, therefore the fraction of the ionised atom can be written as:

x=NINI+NG=NINT

where NT = NI + NG. Write (2) in terms of NT and NI, to get:

NINT-NININT=1n2Ï€mekTh23/2e-I/kT

Multiply the first term in the LHS by NT/NT to get:

NI/NT1-NI/NTNINT=1n2Ï€mekTh23/2e-I/kT

But x=NI/NT,

x21-x=1n2Ï€mekTh23/2e-I/kT

The number of density n can be replaced by P/kT

role="math" localid="1647289106044">x21-x=kTP2Ï€mekTh23/2e-I/kT(3)

04

Calculations

We need to solve this equation for c let the RHS be C, so:

x2=C-xCx2+xC-C=0

Solving the quadratic equation:

x=-C±C2+4C2x=C2+4C-C2x=C1+4/C-12x=kT2P2πmekTh23/2e-I/kT1+4PkT2πmekTh2-3/2eI/kT-1

05

Explanations

(b)To find at what temperature half of the hydrogen atoms will be ionised, we set x= 1/2 into equation (3), to get:

14(1-1/2)=kTP2Ï€mekTh23/2e-I/kT12=kTP2Ï€mekTh23/2e-I/kT

Substitute with

1.0×105PaforP9.11×10-31kgforme1.38×10-23J/Kfork6.626×10-34J·sforh13.6eV=13.7×1.6×10-19=2.176×10-18JforI

To get

12=3.33×10-7K2/5T5/2e-1.577×105K/T

Using python to plot f(T), solve this equation:

f(T)=3.33×10-7K2/5T5/2e-1.577×105K/T-12

The code is shown below, and the solution is the intersection point between the curve and the x axis.

By looking at the graph of f(T) we can see that the curve intersect with x axis at temperature of:

T=25800K

06

Explanation

(c)Because the x is inversely related to the pressure, raising the pressure will raise the temperature in section (b).

This is because when there are fewer particles, there is less pressure, and increasing the pressure, according to Le Chatelier's principle, prevents the ionisation process.

(d)Now we need to plot the result of part (a), using the values in part (6), so:

x=k2P2Ï€mekh23/2T5/2e-I/kT1+4Pk2Ï€mekh2-3/2T-5/2eI/kT-1

Let, t=kTI→T=Itk

so,

x=12P2Ï€meh23/2(It)5/2e-1/t1+4P2Ï€meh2-3/2(It)-5/2e1/t-1

Substitute the values from part (b)

x=1.644×106t5/2e-1/t1+1.216×10-6t-5/2e1/t-1

Plot this function using python, the range of graph is t = 0 to = 0.4, the code is

The graph is:

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Most popular questions from this chapter

The methods of this section can also be applied to reactions in which one set of solids converts to another. A geologically important example is the transformation of albite into jadeite + quartz:

NaAlSi3O8⟷NaAlSi2O6+SiO2

Use the data at the back of this book to determine the temperatures and pressures under which a combination of jadeite and quartz is more stable than albite. Sketch the phase diagram of this system. For simplicity, neglect the temperature and pressure dependence of both ∆S and ∆V.

A formula analogous to that for CP-CVrelates the isothermal and isentropic compressibilities of a material:

κT=κS+TVβ2CP.

(Here κS=-(1/V)(∂V/∂P)Sis the reciprocal of the adiabatic bulk modulus considered in Problem 1.39.) Derive this formula. Also check that it is true for an ideal gas.

Compare expression 5.68 for the Gibbs free energy of a dilute solution to expression 5.61 for the Gibbs free energy of an ideal mixture. Under what circumstances should these two expressions agree? Show that they do agree under these circumstances, and identify the function f(T, P) in this case.

If expression 5.68 is correct, it must be extensive: Increasing both NA and NB by a common factor while holding all intensive variables fixed should increase G by the same factor. Show that expression 5.68 has this property. Show that it would not have this property had we not added the term proportional to In NA!.

Sketch a qualitatively accurate graph of G vs. T for a pure substance as it changes from solid to liquid to gas at fixed pressure. Think carefully about the slope of the graph. Mark the points of the phase transformations and discuss the features of the graph briefly.

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