Problem 1

𝑉 0.6 𝑚3
a) 𝑚𝐴𝑖 = = 3 = 3.2916 𝑘𝑔
𝑣𝐴 𝑖 0.18228 (𝑚 ⁄𝑘𝑔)
𝑆𝐴𝑖 = 6.9534
𝑘𝑗
𝜇𝐴𝑖 = 2785.2 ( ⁄𝑘𝑔)

0.3 𝑚3
𝑚𝐵𝑖 = 3 = 0.27769 𝑘𝑔
1.08034 (𝑚 ⁄𝑘𝑔)
𝑘𝑗
𝜇𝐵𝑖 = 2654.4 ( ⁄𝑘𝑔)

𝑆𝐴𝑖 = 𝑆𝐴𝑓 = 6.9534, 𝑇𝐴𝑓 = 250℃ → 𝑃𝐴𝑓 = 949.56 𝑘𝑃𝑎

𝑚𝐵𝑓 = (𝑚𝐴𝑖 + 𝑚𝐵𝑖 ) − 𝑚𝐴𝑓 = 1.1493 𝑘𝑔

b) 1st Law A+B

𝑄 + 𝑊 = 𝑈2 − 𝑈1

However, 𝑊 = 0 → 𝑄 = 𝑈2 − 𝑈1

𝑄 =(𝑚𝐴𝑓 𝜇𝐴𝑓 + 𝑚𝐵𝑓 𝜇𝐵𝐹 ) − (𝑚𝐴𝑖 𝜇𝐴𝑖 + 𝑚𝐵𝑖 𝜇𝐵𝑖 ) = −320.15 𝑘𝑗

160 kg

R=0.5 m

1.5 mm 1.5 mm
heats up heats up

1 cm diameter

10 μm 10 μm
melts melts

From the 1st law: ∆𝐻ℎ𝑒𝑎𝑡+𝑚𝑒𝑙𝑡 = ∆𝐸𝐾

Heating to melting point:

𝜋
∆𝐻ℎ𝑒𝑎𝑡→𝑚𝑝 = [𝑚]𝑐𝑃 ∆𝑇 = [2(0.0015) (0.01)2 (7800)] (4600)(1460 − 25)
4
= 1217.4 𝐽
𝜋
∆𝐻𝑚𝑒𝑙𝑡 = [𝑚]∆ℎ𝑠𝑙 = [2𝑥10−5 ( ) (0.01)2 (7800)] 270000 = 3.3 𝐽
4
𝜔22 − 𝜔12
→ ∆𝐻𝑡𝑜𝑡𝑎𝑙 = 1220.7 𝐽 = 𝐸𝐾 = 𝐼
2𝑔𝑐
𝑚𝑅 2 2𝜋
where the moment of inertia, 𝐼 = 2
, 𝜔22 = 0 and 𝜔12 = 𝑟𝑝𝑚 ∗ 60 .

60 2 2𝑥2
This leads to (𝑟𝑝𝑚)2 = 1220.7 ∗ (2𝜋) 160(0.5)2
= 11131.45
𝑟𝑒𝑣𝑜𝑙𝑢𝑡𝑖𝑜𝑛𝑠 105.51
𝑟𝑝𝑚 = 105.51 → = =1.76
𝑠 60
 Problem 3
𝜕𝑇 𝜕𝑃 𝑇 𝜕𝑃
a) Using Maxwell equations: (𝜕𝑣 ) = − ( 𝜕𝑠 ) = − 𝑐 (𝜕𝑇 )
𝑠 𝑣 𝑣 𝑣
Need to prove the final equality.
𝜕𝑢 𝜕𝑠 𝜕𝑣
From 𝑐𝑣 = (𝜕𝑇) and recalling 𝑑𝑢 = 𝑇𝑑𝑠 − 𝑃𝑑𝑣 leads to 𝑐𝑣 = 𝑇 (𝜕𝑇) − 𝑃 (𝜕𝑇) .
𝑣 𝑣 𝑣
𝑐𝑣 𝜕𝑠 𝜕𝑣
Thus, = (𝜕𝑇) where of course, (𝜕𝑇) = 0.
𝑇 𝑣 𝑣

𝜕𝑠 𝜕𝑇 𝜕𝑣 𝜕𝑇 1
Next, we use the cyclic relations: (𝜕𝑇) (𝜕𝑣 ) ( 𝜕𝑠 ) = −1 → (𝜕𝑣 ) = − 𝜕𝑠 𝜕𝑣 .
𝑣 𝑠 𝑇 𝑠 ( ) ( )
𝜕𝑇 𝑣 𝜕𝑠 𝑇
𝑐 𝜕𝑇 1 𝑇 1
From our above relation for 𝑇𝑣, we have (𝜕𝑣 ) = − 𝑐 𝜕𝑣 = −𝑐 𝜕𝑣 .
𝑠 ( 𝑣 )( ) 𝑣 ( )
𝑇 𝜕𝑠 𝑇 𝜕𝑠 𝑇

1 𝜕𝑠 𝜕𝑃
Now using Maxwell’s third relation: 𝜕𝑣 = (𝜕𝑣) = (𝜕𝑇 ) , plugging into the above
( ) 𝑇 𝑣
𝜕𝑠 𝑇
𝜕𝑇 𝑇 1 𝑇 𝜕𝑃 𝜕𝑃
equation we have, (𝜕𝑣 ) = − 𝑐 𝜕𝑣 = − 𝑐 (𝜕𝑇 ) = − ( 𝜕𝑠 ) .
𝑠 𝑣 ( ) 𝑣 𝑣 𝑣
𝜕𝑠 𝑇

b) Following the above process we have from Maxwell’s 2nd relation,

𝜕𝑇 𝜕𝑣 𝑇 𝜕𝑣
(𝜕𝑃) = ( 𝜕𝑠 ) = 𝑐 (𝜕𝑇) , where again we must prove the final equality.
𝑠 𝑃 𝑃 𝑃
𝜕ℎ
From 𝑐𝑃 = (𝜕𝑇) , where 𝑑ℎ = 𝑇𝑑𝑠 + 𝑣𝑑𝑃 from this last relationship we have,
𝑃

𝜕ℎ 𝜕𝑠 𝜕𝑃 𝜕𝑃
(𝜕𝑇) = 𝑇 (𝜕𝑇) − 𝑣 (𝜕𝑇 ) . Of course, (𝜕𝑇 ) = 0 and this equation reduces to
𝑃 𝑃 𝑃 𝑃
𝜕ℎ 𝜕𝑠 𝑐𝑃 𝜕𝑠
(𝜕𝑇) = 𝑇 (𝜕𝑇) → = (𝜕𝑇) .
𝑃 𝑃 𝑇 𝑃

𝜕𝑠 𝜕𝑇 𝜕𝑃 𝜕𝑇 1
From the cyclic relations: (𝜕𝑇) (𝜕𝑃) ( 𝜕𝑠 ) = −1 → (𝜕𝑃) = − 𝜕𝑠 𝜕𝑃 .
𝑃 𝑠 𝑇 𝑠 ( ) ( )
𝜕𝑇 𝑃 𝜕𝑠 𝑇

𝑐𝑃 𝜕𝑇 1 𝑇 1
From our above relation for , we have (𝜕𝑃) = − 𝑐 𝜕𝑃 = −𝑐 𝜕𝑃 .
𝑇 𝑠 ( 𝑃 )( ) 𝑣 ( )
𝑇 𝜕𝑠 𝑇 𝜕𝑠 𝑇

1 𝜕𝑠 𝜕𝑣
Using Maxwell’s third relation: 𝜕𝑃 = (𝜕𝑃) = − (𝜕𝑇) , plugging into the above
( ) 𝑇 𝑣
𝜕𝑠 𝑇
𝜕𝑇 𝑇 1 𝑇 𝜕𝑣 𝜕𝑣
equation we have, (𝜕𝑃) = − 𝑐 𝜕𝑃 = 𝑐 (𝜕𝑇) = − ( 𝜕𝑠 ) .
𝑠 𝑃 ( ) 𝑃 𝑃 𝑃
𝜕𝑠 𝑇
 Problem 4

a) 𝑣𝑐 at 𝑇 = 2℃ and 𝑃 = 1 𝑎𝑡𝑚 (air).

𝑐 𝜕𝑃
Note: 𝑣𝑐2 = −𝑣 2 𝑐𝑃 (𝜕𝑣 )
𝑣 𝑇
𝑅𝑇 𝜕𝑃 𝑅𝑇
Assume air is an ideal gas: 𝑃𝑣 = 𝑅𝑇 → 𝑃 = . Thus, (𝜕𝑣 ) = − 𝑣2 . Plugging this
𝑣 𝑇
𝑐𝑃 (1.4)(8.31446𝑘𝐽⁄𝑘𝑚𝑜𝑙−𝐾 )(275.15 𝐾)
into our equation for 𝑣𝑐2 yields → 𝑣𝑐2 = −𝑅𝑇 𝑐 = 𝑘𝑔⁄ =
𝑣 (28.97 𝑘𝑚𝑜𝑙 )
𝑘𝐽
110.5562 ⁄𝑘𝑔 → 𝑣𝑐 = 332.5 𝑚⁄𝑠

b) 𝑣𝑐 at 𝑇 = 2℃ and 𝑃 = 1 𝑎𝑡𝑚 (water). Liquids and solids have fixed volume and
𝑐𝑝
has no effect on pressure so 𝑐𝑝 = 𝑐𝑣 ( 𝑐 = 1).
𝑣
𝑐 𝜕𝑃 𝑣𝑐 𝑣
𝑣𝑐2 = 𝑣 2 𝑐𝑃 (𝜕𝑣 ) = 𝑣𝑐2 = 𝜅 𝑐𝑃 = 𝜅, where from the problem description 𝜅 is the
𝑣 𝑇 𝑣
1 𝜕𝑣
isothermal compressibility 𝜅 = 𝑣 (𝜕𝑃) ,
𝑇

1 1
𝑣𝑐2 = → 𝑣𝑐 = 1405.8 𝑚⁄𝑠
𝑘𝑔⁄ 51.27 𝑥10−6 𝑎𝑡𝑚−1
1000 𝑚3
2𝑑
c) Distance from mother to pup is 2𝑑, so the velocity equals 𝑣𝑒𝑙 = . The time,
𝑡
2𝑑 2𝑑 3 𝑣 ∗𝑣𝑤𝑎𝑡𝑒𝑟
𝑡𝑎𝑖𝑟 − 𝑡𝑤𝑎𝑡𝑒𝑟 = 3 𝑠𝑒𝑐𝑜𝑛𝑑𝑠 = −𝑣 → 𝑑 = 2 (𝑣 𝑎𝑖𝑟 = 653.25 𝑚
𝑣𝑎𝑖𝑟 𝑤𝑎𝑡𝑒𝑟 𝑤𝑎𝑡𝑒𝑟 −𝑣𝑎𝑖𝑟 )

𝑐 𝜕𝑃
d) 𝑣𝑐2 = −𝑣 2 𝑐𝑃 (𝜕𝑣 )
𝑣 𝑇
𝜕𝑃 𝜕𝑣 𝜕𝑠 𝜕𝑃 1
From cyclic relation we have, (𝜕𝑣 ) ( 𝜕𝑠 ) (𝜕𝑃) = −1 → (𝜕𝑣 ) = − 𝜕𝑣 𝜕𝑠 =
𝑠 𝑃 𝑣 𝑠 ( ) ( )
𝜕𝑠 𝑃 𝜕𝑃 𝑣
𝜕𝑃
( ) 𝜕𝑃 𝑇 𝜕𝑃 𝜕𝑣 𝑇 𝜕𝑣
𝜕𝑠 𝑣
− 𝜕𝑣 . We also have, ( 𝜕𝑠 ) = − 𝑐 (𝜕𝑇 ) and ( 𝜕𝑠 ) = 𝑐 (𝜕𝑇) . Inserting into our
( ) 𝑣 𝑣 𝑣 𝑃 𝑃 𝑃
𝜕𝑠 𝑃
𝜕𝑃
𝑐𝑃 (𝜕𝑇)𝑣
equation for 𝑣𝑐2 yields, 𝑣𝑐2 = 𝑣 2 . Using the following cyclic relation
𝑐𝑣 ( 𝜕𝑣 )
𝜕𝑇 𝑃

𝜕𝑣 𝜕𝑃
𝜕𝑃 𝜕𝑇 𝜕𝑣 𝜕𝑣 ( ) 𝜕𝑃 ( )
𝜕𝑇 𝑃 𝜕𝑇 𝑣
(𝜕𝑇 ) (𝜕𝑣 ) (𝜕𝑃) = −1 → (𝜕𝑃) = − 𝜕𝑃 → (𝜕𝑣 ) = − 𝜕𝑣 . Now we use this
𝑣 𝑃 𝑇 𝑇 ( ) 𝑇 ( )
𝜕𝑇 𝑣 𝜕𝑇 𝑃
𝜕𝑃
latter form of the equation for (𝜕𝑣 ) in our equation for 𝑣𝑐2 , which leads to,
𝑇
𝜕𝑃
𝑐 (𝜕𝑇) 𝑐 𝜕𝑃
𝑣𝑐2 = 𝑣 2 𝑐𝑃 𝜕𝑣 𝑣 = −𝑣 2 𝑐𝑃 (𝜕𝑣 ) , which completes the derivation.
𝑣 ( ) 𝑣 𝑇
𝜕𝑇 𝑃
 Problem 5
𝜕𝑃
a) We must find (𝜕𝑇 ) . Starting from the product rule (cyclic rule) we have,
𝑣
𝜕𝑃 𝜕𝑣 𝜕𝑃
(𝜕𝑇 ) = − (𝜕𝑇) (𝜕𝑣 ) . By definition we have,,
𝑣 𝑃 𝑇

1 𝜕𝑣 1 𝜕𝑣
𝛼𝑃 = 𝑣 (𝜕𝑇) and 𝜅𝑇 = 𝑣 (𝜕𝑃) . Putting this together we can easily obtain,
𝑃 𝑇

𝜕𝑃 𝛼𝑃
1.8 𝑥 10 −5
(𝜕𝑇 ) = = 5.32 𝑥 10−6 = 33.8 𝑏𝑎𝑟⁄℃ . Assuming 𝛼𝑃 𝜅𝑇 and by integrating this
𝑣 𝜅 𝑇
equation we have,
𝛼𝑃
∆𝑃 = ∆𝑇 and for ∆𝑇 = 1℃, yields ∆𝑃 = 33.8 𝑏𝑎𝑟.
𝜅𝑇
 Problem 6
𝐺
At equilibrium 𝑓𝑠𝑜𝑙 𝐿
= 𝑓𝑠𝑜𝑙 , where 𝑠𝑜𝑙 stands for solute. At constant pressure a
change in temperature can be written as,
𝐺 𝐿
𝑑(ln 𝑓𝑠𝑜𝑙 ) 𝑑(ln 𝑓𝑠𝑜𝑙 )
( ) 𝑑𝑇 = ( ) 𝑑𝑇.
𝑑𝑇 𝑑𝑇
𝑃 𝑃

𝐺
Because the solvent is non-volatile, 𝑓𝑠𝑜𝑙 (constant pressure) depends only on 𝑇 (gas
composition is constant). On the other hand, 𝑓𝑠𝑜𝑙𝐿
(at constant pressure) depends on
𝐿
𝑑(ln 𝑓𝑠𝑜𝑙 )
both 𝑇 and composition 𝑥𝑠𝑜𝑙 ). Thus we can write ( ) 𝑑𝑇 as,
𝑑𝑇
𝑃

𝐿 𝐿
𝑑(ln 𝑓𝑠𝑜𝑙 ) 𝑑(ln 𝑓𝑠𝑜𝑙 ) 𝑑(ln 𝑓 𝐿 )
( 𝑑𝑇
) 𝑑𝑇 = ( 𝑑𝑇
) 𝑑𝑇 + (𝑑(ln 𝑥𝑠𝑜𝑙 )) 𝑑(ln 𝑥𝑠𝑜𝑙 ).
𝑃 𝑃,𝑥 𝑠𝑜𝑙 𝑇,𝑃

In addition, we have,
𝐺 0 𝐺
𝑑(ln 𝑓𝑠𝑜𝑙 ) ℎ𝑠𝑜𝑙 − ℎ𝑠𝑜𝑙
( ) =
𝑑𝑇 𝑃
𝑅𝑇 2
𝐿 )
𝑑(ln 𝑓𝑠𝑜𝑙 0
ℎ𝑠𝑜𝑙 − ℎ̅𝑠𝑜𝑙
𝐿
( ) =
𝑑𝑇 𝑃
𝑅𝑇 2
where
0
ℎ𝑠𝑜𝑙 : ideal gas enthalpy of solute
𝐺
ℎ𝑠𝑜𝑙 : real ideal gas enthalpy of solute
ℎ̅𝑠𝑜𝑙
𝐿
: partial molar enthalpy of solute in the liquid phase.

Next, we will assume we can use Henry’s law thus,

𝑓𝑠𝑜𝑙
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑥𝑠𝑜𝑙
𝐿
𝑑(ln 𝑓𝑠𝑜𝑙 )
( ) = 1.
𝑑(ln 𝑥𝑠𝑜𝑙 )
𝑇,𝑃

Substituting our 2nd, 3rd, 4th and 5th equation into our 1st equations yields,
𝑑(ln 𝑥𝑠𝑜𝑙 ) ∆ℎ̅𝑠𝑜𝑙
( ) =
1 𝑅
𝑑 (𝑇)
𝑇,𝑃

𝐺
Physically, ℎ𝑠𝑜𝑙 > ℎ̅𝑠𝑜𝑙
𝐿
and therefore, 𝑥𝑠𝑜𝑙 decreases with increasing temperature.
(This is true for most cases but it is not always true)