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Linode as a platform can scale to meet your needs, but as your application grows more and more, the complexity (or at least emphasis on) the load balancing solution will also scale. That's not a Linode thing, just a fundamental factor of very large scale applications. Is your application already designed to scale to multiple machines? You would want to have multiple database backend servers, multiple application servers, multiple front-end HTTP servers (although you could mix this with the application servers), etc.
It's not the sort of thing that can be done without modification to the web service, because there are a bunch of factors on multi-server applications that don't happen when everything lives on one box (or one application box and one sql box). Stuff like which server has the client's session data, how you handle multiple database servers, the differences you face when your PHP script isn't running on the same box as what accepted the initial HTTP connection such as what remote IP you see, etc.
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