What is the new boiling temperature for bromine, if the pressure changes from atmospheric pressure to "76000 Pa"?

To what temperature do we need to heat up bromine in order for it to boil on 76 000 Pa. At atmospheric pressure bromine boils on 58 degrees.
Enthalpy of vaporization for bromine is "194.26 J/g".

1 Answer
Jan 1, 2017

I got color(blue)(T_(b2) ~~ 50.5^@ "C"), when I used T_(b1) = 58.8^@ "C" and your DeltaH_"vap" of "194.26 J/g", or DeltabarH_"vap" = "31.04 kJ/mol". But that's not the DeltabarH_"vap" I see here.

  • If you use T_(b1) = 58^@ "C" and DeltabarH_"vap" = "31.04 kJ/mol", you should get T_(b2) ~~ 49.8^@ "C".
  • If you use T_(b1) = 58^@ "C" and DeltabarH_"vap" = "29.96 kJ/mol", you would get T_(b2) ~~ 49.5^@ "C".
  • If you use T_(b1) = 58.8^@ "C" and DeltabarH_"vap" = "29.96 kJ/mol", you would get T_(b2) ~~ 50.2^@ "C".
    This demonstrates how good the assumption is that DeltaH_"vap" doesn't vary in this temperature range.

So basically, you should get somewhere between 49.5^@ "C" and 50.5^@ "C".


Since we need to find a new temperature given two pressures, one temperature, and an enthalpy of vaporization DeltaH_"vap", we should turn to the Clausius-Clapeyron equation in its natural logarithm form.

bb(ln(P_2/P_1) = ln((P(T_(b2)))/(P(T_(b1)))) = -(DeltabarH_"vap")/R[1/T_(b2) - 1/T_(b1)]),

where P(T_(bi)) is the vapor pressure of the substance at some specified boiling point T_(bi), DeltabarH_"vap" is the molar enthalpy of vaporization, in "kJ"/"mol", and R = "0.008314472 kJ/mol"cdot"K" is the universal gas constant.

To use it, we're solving for T_(b2). It's generally easier to plug in numbers early, actually.

Recall that atmospheric pressure is cancel"1 atm" xx "101325 Pa"/cancel"atm" = "101325 Pa". So, P_1 = "101325 Pa", and:

ln("76000 Pa"/("101325 Pa")) = -(194.26 xx 10^(-3) "kJ"/cancel"g" xx (2xx79.904 cancel"g")/("mol Br"_2))/("0.008314472 kJ/mol"cdot"K")[1/T_(b2) - 1/(58.8 + "273.15 K")]

=> ln(0.7501) = -(31.044 cancel"kJ/mol")/(0.008314472 cancel"kJ/mol"cdot"K")[1/T_(b2) - 1/"331.95 K"]

= -"3733.77 K"[1/T_(b2) - 0.0030125 "K"^(-1)]

=> -ln(0.7501)/"3733.77 K" = 1/T_(b2) - 0.0030125 "K"^(-1)

=> -ln(0.7501)/"3733.77 K" + 0.0030125 "K"^(-1) = 1/T_(b2)

=> T_(b2) ~~ "323.68 K",

or about color(blue)(50.5^@ "C").

This should make physical sense because we say that boiling is easier at higher altitudes, at which the pressure is lower.

Lower pressure makes it easier to achieve the required vapor pressure, and thus, it is easier to boil at higher altitudes.

I derive the Clausius-Clapeyron equation below, if you want to take a look.


DISCLAIMER: DERIVATION BELOW!

I never remember the Clausius-Clapeyron equation, but I do remember the Clapeyron equation, so we can derive it by comparing with the Clapeyron equation:

bb((dP)/(dT) = (DeltaH_"vap")/(TDeltaV^((l)->(g))))

where DeltaV^((l)->(g)) is the change in volume due to vaporization, and T is temperature in "K". This equation tells you the slope of the liquid-vapor coexistence curve on a phase diagram.

Since a gas is much more compressible than a liquid, we can say that DeltaV^((l)->(g)) ~~ V_(gas). Therefore:

(dP)/(dT) ~~ (DeltaH_"vap")/(TV_(gas))

If the gas is assumed ideal, then we can further substitute the ideal gas law to get that V_(gas) = (nRT_b)/P, and:

(dP)/(dT) ~~ (DeltaH_"vap"P)/(nRT_b^2)

= (DeltabarH_"vap"P)/(RT_b^2)

Recall that the Clausius-Clapeyron equation has (dlnP)/(dT) on the left side. From the chain rule, (dlnP)/(dT) = (dlnP)/(dP)(dP)/(dT) = 1/P(dP)/(dT).

So, we obtain the Clausius-Clapeyron equation:

1/P(dP)/(dT) = color(green)((dlnP)/(dT) = (DeltabarH_"vap")/(RT_b^2))

where DeltabarH_"vap" = (DeltaH_"vap")/n is the molar enthalpy of vaporization of "Br"_2(l).

Now, when we integrate both sides (the left side varies from P_1 to P_2, and the right side varies from T_(b1) to T_(b2)), and assume that DeltabarH varies little in this temperature range, we get:

int_(P_1)^(P_2) dlnP

= int_(T_(b1))^(T_(b2))(DeltabarH_"vap")/(RT_b^2)dT_b = (DeltabarH_"vap")/Rint_(T_(b1))^(T_(b2))1/(T_b^2)dT_b

=> bb(ln(P_2/P_1) = -(DeltabarH_"vap")/R[1/T_(b2) - 1/T_(b1)])

This is the equation we'd use to solve this problem.