Frost Diagrams A plot of nE for the couple X(n)/X(0) vs.

oxidation number (n) of the element: X(n) + ne- X0 nE = -rG/F E

Frost Diagrams What information can one obtain from a Frost diagram? Lower = more thermodynamically stable Convex = disproportionation Concave = comproportionation Upper left = strong oxidising agent in this diagram Upper right= reducing agent in this diagram

Frost diagram for Mn

Frost Diagrams Can be constructed from Latimer diagrams

Example
Construct a Frost diagram from the following Latimer diagram (in aq acidic solution) +1.25 -0.34

Tl3+

Tl+
+0.72

Tl

3 nEo 2

-1 0 1 2 3 4 N

Note that in general n2Eo2

n2Eo2 n1Eo1 Eo = n2 n1 I.e. slope = E

nEo

n1Eo1

n1 N

n2

Tl+ is the most stable oxidation state Tl3+ is a strong oxidising agent because slopes of the lines to the other two states are large and positive

See SA pp. 155-158

Example From the Frost diagram for N below, estimate E for the NO3- | NO2- couple in acidic media (red line):

Example