Sometimes the section of snake chain next to the cap melts and becomes inflexible. You've gotta do it as quick as possible and focus mostly on the cap as the chain heats quickly. Quite a few times I ended up with either an over soldered and melted chain or the cap just came off when I gave it a little pull (too much or too little!)... it might be easier working in a larger scale though. Its been a while since I've done it so I hope this is all correct! Never seen 5mm snake chain, thats huge!
A little rouge applied to the area adjacent to the area to be soldered can act as an inhibitor. As Charlotte said, it is a hit and run. Try to focus the heat below the hole though as because it does not benefit from the chain as a heat sink this tends to collapse very easily. Alternatively, try placing insulated tweezers through the hole. I tend to flux and solder coat the end of the snake chain first applying the rouge. Sand any bumps to create a tight fit, reflux and place the end cap over and heat.
Thanks folks, cookies have just started the 5mm chain, which is good as i've just tried to repair a silverplated one, which was like silverplatted butter.
I was begining to think that i'd just heat the end caps and hope the easy solder on the chain would melt before it did. Just ordered easy solder paste hopping that it might make life easier..
I'll let you know how I get on in a few days time.
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