I've never soldered or worked with bare metal before and thought this might be a good pedagogical project. I bought the a Weller WLC100 and some SchmartSolder. My first attempt I set the unit to 5 (max power), waited a minute, set it to 3, waited a minute and pressed the tip against the solder. It went up in smoke instantly, I'm assuming it is too hot. I brought the temperature down to 2 and it still burnt off, though not as quickly. Any suggestions, what temperature (1-5 number) should I be soldering at? Also. how straight do the breakway headers have to be when soldered on? I assumed very straight, but I had a hard time holding them in place, is a third hand tool necessary? Also is the board ruined? Did I "burn away" anything? Thanks, I thought this would be the easy party.

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You should Google "soldering tutorial" - the first few hits will be VERY helpful. There is a lot to learn, so study the tips, and practice, practice, practice, practice! The smoke you see is probably the rosin/flux core - not the solder itself. The idea is that when you heat a joint and melt the solder in, the flux melts as well and paves the way for a good joint. It's a little trickier than that, but that's a fair description I think. Some keys: clean surfaces to solder too, a clean tip, maybe a little flux (or just the flux of the rosin core solder), decent heat, and good lighting. In reality you can probably make a fine joint with the heat set anywhere above the melting temperature of the solder. It just might take more or less time and if you're too hot, it'll stress the more sensitive components. Regarding the breakaway headers - only as straight as you want them! They certainly do not need to be perfectly straight, although it is helpful if they the plastic part is down touching the board to provide some mechanical rigidity when you connect/disconnect to them.
Watch this video and practice before you ruin your board.
http://www.youtube.com/watch?v=I_NU2ruzyc4&feature=fvw

Try using tape to hold components in place.
Dump the Schmartsolder - I bought a couple of packs and got the same result as you and actually by the time you have fiddled with the rings trying to get them on your finger you could have finished soldering the component normally. Soldering is not rocket science and as the other guys have said there is lots of support on the web. Also take a look at Sparkfun and Ladyada tutorials.

To get the headers straight I use spare lengths of the oppsite gender to plug them into and if there are holes on the other edge of the board you can make a square/grid of the headers and they are held perpendicular to the board while you solder them.

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