Chromate Production

The chromate ion is kinda fun. Maddeningly

yellow or orange, it has a strong color. It is a
reasonable oxidizer. Many of its salts are
insoluble, allowing corrosion-resistant
coatings (such as the golden-iridescent zinc
dichromate finish on many steel parts) and
strong pigments (lead chromate a prime
example). And to top it all off, it's a known
carcinogen, so it's biologically exciting too!
Too bad it's not something found at the
hardware store. I could probably find it, but
screw that, I like making things. So how to do
it? Well, you need a strong oxidizer to start
with, which isn't much of a problem since
we're all breathing an excellent one. Oxygen
doesn't do chemistry very well though.
Hypochlorite is a more accessible one, and
works quite nicely. What of the chrome in the
first place? There's about 10-20% in any
random chunk of stainless steel, but bleh,
what a mess to seperate. Can always go grab
some Cr2O3 at the pottery store. Happens
that I have some on hand from that source.
But uh, thing is, this shit is refractory. It
doesn't dissolve worth jack. I need something
a lot more aggressive. How about a bath of
molten hydroxide? MMMMM that might do it!
My chosen reaction is: Cr2O3 + 4 NaOH +
KClO3 + 3 KCl = 2 K2CrO4 + 4 NaCl + 2 H2O.
The atomic weights are 152 + 122.5 + 223.5
+ 160 = 388 + 234 + 36, respectively. I
chose to use this combination because I have
NaOH and not KOH, and KClO3 or NaClO3 but
no KNO3. I chose KClO3, and added extra KCl
since I want K2CrO4 to come out of solution,
either after fusing or after recrystallizing from
water. The mixture needs to be fractionally
crystallized (salt will crystallize first), or
modified for dichromate instead (potassium
dichromate's solubility is on par with
potassium chlorate).
"Actions and Observations"

Here are the weighed chemicals (give or take

0.1 g) laid out on a sheet of paper. 14.9 g
Cr2O3, 15.1 g KClO3, 20.0 g KCl and 17.5 g
NaOH. The Cr2O3 is greener in person, I just
didn't get a great picture of it.

All the chemicals, mixed and waiting in the

crucible. This is one application of my still-in-
development induction heater. I can't get
much power into this relatively large crucible,
but it's enough to melt this mixture.

       
These three pictures show the green slop. As
the temperature rises, first the NaOH melts
and the chrome disperses, making a thickly
green liquid. Then things start dissolving. For
instance, sodium chromite may be formed:
Cr2O3 + 2 NaOH = Na2Cr2O4 + H2O (or other
stoichiometries). As the reaction progresses,
steam is liberated, which must be controlled
carefully. The reaction appears to be slightly
exothermic, so I started this fusion with no
kaowool surrounding the crucible. I controlled
the temperature carefully (with the heater's
voltage control) and stirred constantly to
make sure it didn't boil over. In the middle
picture, the mixture is bubbling smoothly (but
not to be left unattended without stirring!).
After about ten minutes at the same
temperature, the steam is mostly gone and it
begins to thicken. The rightmost picture
shows the globby product at this point.

       
Once it thickens, the steam is just about done
and stirring only needs to be done to keep the
mixture evenly heated. Since it's not in
danger of boiling over, I cranked the heat.
Pretty soon, it spontaneously starts turning
orange, probably a more exothermic reaction
(especially with a chlorate oxidizer). In the
left picture you see what looks like orange
glow, but is actually reflected light from the
chromate that is forming. In the middle
picture, the reaction is essentially complete, a
few minutes after the mixture thickened.
Throughout the oxidation, the walls don't heat
up much (being solid steel), so I heat it to the
melting point to homogenize the reactants. (I
put some kaowool back in around the crucible
to help it heat up.) The remarkable thing is,
chromate is thermochromic: it melts to a deep
red, dense liquid. The color is almost blood
red, but blood is too bright; this is much
darker. I can tell it is dense because the
coarsely ground potassium chloride I added
floats on top, until it dissolves at a somewhat
higher temperature (maybe 1000°F, around
the threshold of visible incandescence, which
has about the same color as the reflected light
from this liquid!).
At that peak temperature, the liquid is quite
mobile (not as mobile as NaCl fortunately)
and pours easily.

Some of the cooled product. It breaks up (due

to the stress, loudly!) if left alone while
cooling. The most dramatic thing to be seen in
these two pictures is the color change, back
from deep red, to orange, to a canary yellow
with almost a tint of green.
What remains? I will dissolve this in water and
recrystallize it. I may add a little HCl to form
the deep orange dichromate instead. The
optimal reaction for dichromate, using these
reagents, uses only one mole of KCl, since the
final product has the formula K2Cr2O7. No
need for excess potassium ion.