equilibrium and radioactivity from there to here, from here to there, funny things are everywhere...
TRANSCRIPT
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Equilibrium and Radioactivity
From there to here, from here to there, funny things are everywhere
--TSG 1957
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The rate of a reaction
• Expressed in mol/sec or M/s
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N2 + 3H22NH3
• If 2.40 moles of NH3 are produced each second, what is the rate of use of N2 and H2?
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N2 + 3H22NH3
• If 2.40 moles of NH3 are produced each second, what is the rate of use of N2 and H2?
• 2.40 mol NH3/s x 1 N2/2 NH3
=1.20 mol N2/s
• 2.40 mol NH3/s x 3 H2/2 NH3
=3.60 mol H2/s
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How can you speed up a reaction?
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How can you speed up a reaction?
• --Heat it up.
• --Crush, grind or powder a solid reactant.
• --Increase pressure of a gaseous reactant
• --Increase concentrations of aqueous reactants
• --Add a catalyst (if known)
• (Stir or shake to bring reactants together.)
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How would you speed up…
• Hydrochloric acid acts on tin metal to form hydrogen gas and aqueous tin (II) chloride
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How would you speed up…
• Hydrochloric acid acts on tin metal to form hydrogen gas and aqueous tin (II) chloride
• Increase concentration of HCl
• Powder the tin
• Heat the reactants
• Stir or shake
• (I don’t know of a catalyst—it’s pretty fast already)
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Reversible reactions.
• AKA “all reactions”
• All reactions work in reverse, at least a little bit.
should be written as
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Write the reverse reaction
• 2NaHCO3 (s) Na2CO3 (s) + H2O (g)
• CaCO3 (s) CaO (s) +CO2 (g)
• H2 (g) +Cl2 (g) 2HCl (g)
• N2 (g) + 3H2 (g) 2NH3 (g)
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H2 +I2 2HI
1 mole H2
and 1 mole I2
(1L)
If you start with 1 mole H2 and 1 mole I2 in a 1L flask…
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H2 +I2 2HI
1 mole H2
and 1 mole I2
(1L)
.8 mole H2 .8 mole I2
and .4 mole HI
(1L)
…it will proceed forwards. Some of the reactants will form products.
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H2 +I2 2HI
2 mole HI
(1L)
If you start with 2 moles HI in a 1L flask…
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H2 +I2 2HI
2 mole HI
(1L)
.8 mole H2 .8 mole I2
and .4 mole HI
(1L)
…it will proceed in reverse. Some of the “products” will form reactants
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H2 +I2 2HI
1 mole H2
and 1 mole I2
(1L)
2 mole HI
(1L)
Did you notice?
.8 mole H2 .8 mole I2
and .4 mole HI
(1L)
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H2 +I2 2HI
1 mole H2
and 1 mole I2
(1L)
2 mole HI
(1L)
You get the same final concentrations
.8 mole H2 .8 mole I2
and .4 mole HI
(1L)
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Starting with reactants…
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0 20 40 60
The forward reaction starts out fast, then slows as reactants are used up
Rat
e of
rea
ctio
n (m
ol/s
)
Time (s)
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Starting with reactants…
The reverse reaction starts out at 0 mol/s, then speeds up as products are produced
0
0.005
0.01
0.015
0.02
0.025
0 20 40 60
Rat
e of
rea
ctio
n (m
ol/s
)
Time (s)
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Starting with reactants…
Did you notice?
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0 10 20 30
Rat
e of
rea
ctio
n (m
ol/s
)
Time (s)
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Starting with reactants…
The forward and reverse reactions reach the same rate. Concentrations will stabilize
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0 10 20 30
Rat
e of
rea
ctio
n (m
ol/s
)
Time (s)
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Eventually…
…reactants make products just as fast as products make reactants.
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Eventually…
…reactants make products just as fast as products make reactants.
• It’s inevitable.
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Eventually…
…reactants make products just as fast as products make reactants.
• It’s inevitable.
• It’s dynamic equilibrium
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Try it.
• N2 + 3H2 2NH3
• Describe the rate of the forward reaction if you start with nitrogen and hydrogen.
• What is the rate of the reverse reaction?
• What happens to each rate?
• Why?
• Eventually…
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The equilibrium constant expression
• For aA +bB cC + dD
(if all substances are gasses or aqueous)
• The expression
[C]c [D]d
[A]a [B]b is a constant (K) at a given temperature
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Please note:
• Products on top
• Coefficients become exponents
• Brackets mean “molarity”
• Concentrations are multiplied
• Solid and liquid substances are not included
…then this ratio is a constant!
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For example
• For: H2(g) +I2 (g)2HI (g)
• The equilibrium constant expression is:
• K= [HI]2 = (.4M)2 = .25
[H2][I2] (.8M)(.8M)
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Write the equilibrium constant expression for …
1) 4NH3(g)+5O2(g)4NO(g)+6H2O(g)
2) CO (g) + 2H2 (g) CH3OH (g)
3) NH3(g)+H2O (l) NH4+ (aq) + OH-(aq)
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Rookie mistakes:
• --putting reactants on top• --using coefficients inside the brackets• --adding instead of multiplying
concentrations• --multiplying by coefficients, instead of
raising to the power• --including liquids and solids.
Avoid these errors!
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What is the value of K?
1) 4NH3(g)+5O2(g)4NO(g)+6H2O(g)
.050 M .30 M .20 M .40 M
2) CO (g) + 2H2 (g) CH3OH (g)
.20 M .20 M .030 M
3) NH3(g)+H2O (l) NH4+ (aq) + OH-(aq)
.10 M 55.5 M .0013 M .0013 M
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What is the unknown concentration?
1) 4NH3(g)+5O2(g)4NO(g)+6H2O(g)
.060 M .40 M .15 M ? M
2) CO (g) + 2H2 (g) CH3OH (g)
? M .25 M .070 M
3) NH3(g)+H2O (l) NH4+ (aq) + OH-(aq)
? M 55.5 M .0019 M .00030M
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Le Chatelier’s Principle
If a system in equilibrium is subjected to a stress, the system will shift in the direction that will relieve that stress
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Application of LeChatelier’s principle
• “Shift right”--forward reaction is faster, --more of all products are formed--all reactants are used
• “Shift left”--reverse reaction is faster, --more of all reactants are formed--all products are used
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Application of LeChatelier’s principle
• An aqueous or gas substance in the reaction added—shift away to use it up
• Increasing pressure—shift toward side with fewer moles of gas to relieve pressure
• Increasing temperature—shift in the endothermic direction to absorb heat
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N2(g) + 3H2(g) 2NH3(g) + Which way would the equilibrium
shift if you:1. Add N2(g)
2. Add H2(g)
3. Add NH3(g)
4. Increase P (compress)
5. Increase T
6. Add a catalyst
7. Remove N2(g)
7. Remove H2(g)
8. Remove NH3(g)
9. Decrease P (allow to expand)
10. Decrease T
11. Increase pressure by adding He (g)
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N2(g) + 3H2(g) 2NH3(g) + Which way would the equilibrium
shift if you:1. Add N2(g)
2. Add H2(g)
3. Add NH3(g)
4. Increase P (compress)
5. Increase T
6. Add a catalyst
7. Remove N2(g)
7. Remove H2(g)
8. Remove NH3(g)
9. Decrease P (allow to expand)
10. Decrease T
11. Increase pressure by adding He (g)
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N2(g) + 3H2(g) 2NH3(g) + Why?
1. Add N2(g)
2. Add H2(g)
3. Add NH3(g)
4. Increase P (compress)
5. Increase T
6. Add a catalyst
7. Remove N2(g)
7. Remove H2(g)
8. Remove NH3(g)
9. Decrease P (allow to expand)
10. Decrease T
11. Increase pressure by adding He (g)
Forward reaction
speeds up
Reverse reaction
slows down
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How would you shift this reaction to the left?
HCOOH (aq)+ HCOO- (aq) + H+ (aq)
(formic (heat) (formate (hydrogen
acid) ion) ion)
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Why do reactions proceed at all?
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Why do reactions proceed at all?
• To go to a more stable, lower energy state.
1) If H is (-), reaction gives off heat. (H<0)
OR
2) an advantage in gaining entropy, S. (S>0)
OR BOTH!
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Enthalpy and Entropy
H
• Endo- or exothermic
• Energy is stored in/released from chemical bonds
• Measured in kJ/mol
S
• Gains or loses entropy
• A system becomes more or less disordered (s<l<aq<<g)
• Measured in J/ mol k
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2H2 +O22H2O…
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2H2 +O22H2O…
• H is very negative—it gives up a lot of heat.
2H2 +O22H2O +
Releasing heat is an advantage for a reaction
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2H2 +O22H2O…
• S is also negative—it loses entropy as 3 moles of gasses form only 2 moles.
This is a disadvantage, it’s worse at higher temperatures. Over 5000oC, hydrogen gas won’t even burn.
The advantage for entropy depends on temperature
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What is H, S and G?
• + CaCO3 (s) CaO (s) +CO2 (g)
• H2 (g) +Cl2 (g) 2HCl (g) +
• N2 (g) + 3H2 (g) 2NH3 (g) +
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• What happens at a higher temperature?
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…at a higher temperature…
1) Particles move faster.
2) There are more collisions.
3) Those collisions have more energy.
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To react, reactants must collide with enough energy, the activation energy.
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Cool, medium, warm
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Notice:
1) The bell-shaped distributions
2) The average speed is higher at higher To
3) The speeds spread out more at higher To
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What is “fast enough” to react?
More collisions will have enough energy to react at higher temperatures
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What if this is “fast enough”?
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What if this is “fast enough”?
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To react, reactants must collide with enough energy, the activation energy.
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Catalysis
• A catalyst speeds up a reaction
• This is done by lowering the energy barrier, Ea
• When the barrier is lower, more collisions are “fast enough”
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Nuclear Chemistry--
--as opposed the the unclear chemistry you have studied
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Nuclear Chemistry
• --breaks the rules that one atom cannot be converted to another.
Chemistry: the dance of the electrons —nuclear reactions change the nuclei of atoms
• --charge and mass are still conserved.
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Nuclide Notation
• A nuclide is a nucleus or atom of a specific isotope of an element
K39
19
• Potassium-39.
-- has 19 protons (atomic number = 19), making it potassium, and 20 neutrons (making a mass number of 39)
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How many p, n, e- in each?What is the mass number and
atomic number?
Cl-36
17
Sr+290
38
I-131
53
Th228
90
H3
1
Fe+359
26
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How many p, n, e- in each?What is the mass number and
atomic number?
Cl-36
17
Sr+290
38
I-131
53
Th228
90
H3
1
Fe+359
26
undergoes a decay
undergoes an decay
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Natural decays
• —the loss of particle from a nuclide--The particle is composed of 2p and 2n,
the 4He nucleus--decreases the mass by 4 and the atomic
number by 2• —emission of an electron ( particle) from the
nucleus by the conversion of a n p + e---the electron is the particle--increases the atomic number by 1, does
not affect mass
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Write the reaction
• Argon-39 undergoes a decay
• Thorium-228 undergoes an decay
• An decay forms lead-204
• A decay forms nitrogen-14
• A natural decay forms Sc-45 from Ca-45
• A natural decay forms Ac-227 from Pa-231
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Stable?
![Page 66: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/66.jpg)
Nuclear reactions
• Many nuclear reactions involve colliding nuclei or smaller particles at some significant fraction of the speed of light,
• --find the missing particle by balancing mass and charge.
![Page 67: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/67.jpg)
Fission vs Fusion• Fission=breaking up large nuclei—
--natural radioactive decay of large atoms --used for nuclear power
• Fusion=combining small nuclei --occurs naturally in stars --prospects for nuclear energy—no radioactive byproducts
Both are transmutations—one nuclide is converted into another
![Page 68: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/68.jpg)
Consider the relationships
• Half life
• Original amount
• Final amount
• Time elapsed
![Page 69: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/69.jpg)
Consider the relationships
A=A0(1/2)
• A is the amount of the sample remaining
• A0 is the original amount in the sample
• t is the time that has passed, and
• t 1/2 is the half-life of the nuclide
t/t1/2
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Please notice
A=A0(1/2)
A / A0 = the fraction remaining and
t / t 1/2=the number of half-lifes that have passed
t/t1/2
![Page 71: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/71.jpg)
Try it.
• Hydrogen-3 has a half life of 12.3 years. If you start with a 20 g sample of H-3
--how much is left after 12.3 years?
--how much is left after 24.6 years?
--how much is left after 30.2 years?
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Try it.
• Br-82 has a half life of 35.3 hours. If you start with a 6.5 mg sample of Br-82
--how much is left after 4 days?
--how long will it take to reach .75 mg?
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Try it.
• Br-82 has a half life of 35.3 hours. If you start with a 6.5 mg sample of Br-82
--how much is left after 4 days?
--how long will it take to reach .75 mg?
How do you solve for an exponent?
![Page 74: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/74.jpg)
Use a log function
log (A/A0)= log(1/2)
log (A/A0)= log(1/2)
= log (A/A0) log(1/2)
t/t1/2
t/t1/2
t/t1/2
![Page 75: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/75.jpg)
Try it.
• Br-82 has a half life of 35.3 hours. If you start with a 6.5 mg sample of Br-82
--how much is left after 4 days?
--how long will it take to reach .75 mg?
![Page 76: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/76.jpg)
Try it.
• If you start with 1.38 mg of U-234 and t1/2=2.44 x 105 yrs for its decay:
--how much is left after 20,000 years?
--how long will it take to reach 0.40 mg?
![Page 77: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/77.jpg)
Try it.
• A .350 mg sample of K-42 decays to only .066 mg in 29.7 hours.
--what is the half life?
--how much was left after 20.0 hours?
--how long will it take to reach .010 mg?
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The uses of radioactivity
![Page 79: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/79.jpg)
The uses of radioactivity
• Medicine—tracers, radiation therapy
• History/geology—radioisotope dating
• Nuclear energy
• Nuclear weapons
![Page 80: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/80.jpg)
The uses of radioactivity
• Medicine—
Tracers:
I-131, S-35, F-18, P-32
Radiation therapy
I-131, Lu-177, Y-90, Sr-89
![Page 81: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/81.jpg)
The uses of radioactivity
• History/geology—radioisotope dating
• C-14, U-238, Sm-147, K-40
![Page 82: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/82.jpg)
The uses of radioactivity
• Nuclear Energy
• Nuclear reactions give off a large amount of energy
• This energy is often converted to electricity
• A nuclear reactor contains the reactants so the by-products (usually neutrons) carry out the chain reaction
![Page 83: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/83.jpg)
Pressurized water reactor
![Page 84: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/84.jpg)
Boiling water reactor
![Page 85: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/85.jpg)
Heavy water reactor
![Page 86: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/86.jpg)
Gas-cooled reactor
![Page 87: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/87.jpg)
Hydride salt reactor
![Page 88: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/88.jpg)
Pebble bed modular reactor
![Page 89: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/89.jpg)
![Page 90: Equilibrium and Radioactivity From there to here, from here to there, funny things are everywhere --TSG 1957](https://reader031.vdocument.in/reader031/viewer/2022012918/56649e165503460f94b017e0/html5/thumbnails/90.jpg)
NERVA